Guidelines For Shutdown Layup and Starting For Combined Cycle

Cycle Chemistry Guidelines for Shutdown,
Layup, and Startup of Combined Cycle

Units with Heat Recovery Steam Generators
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Cycle Chemistry Guidelines for
Shutdown, Layup and Startup of
Combined Cycle Units with Heat
Recovery Steam Generators
1010437
Final Report, March 2006
EPRI Project Manager

K. Shields
Electric Power Research Institute • 3412 Hillview Avenue, Palo Alto, California 94304 • PO Box 10412, Palo Alto, California 94303 • USA
800.313.3774 • 650.855.2121 • askepri@epri.com • www.epri.com
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CITATIONS
This report was prepared by
Electric Power Research Institute (EPRI)

3420 Hillview Avenue
Palo Alto, CA 94304
Authors
K. Shields
B. Dooley
A. Aschoff
M. Ball
This report describes research sponsored by EPRI.
The report is a corporate document that should be cited in the literature in the following manner:
Cycle Chemistry Guidelines for Shutdown, Layup and Startup of Combined Cycle Units with
Heat Recovery Steam Generators, EPRI, Palo Alto, CA: 2006. 1010437.
iii
PRODUCT DESCRIPTION
Complete optimization of cycle chemistry in a combined-cycle unit requires more than proper
selection and optimization of operating chemistry. Protection of the steam-water cycle also is
essential during shutdown, layup, and startup phases. These guidelines consider protection of
steam- and water-touched components at these times, consistent with the operating cycle
chemistries in use.
Results & Findings

These guidelines have been developed specifically for use with Cycle Chemistry Guidelines for
Combined Cycle/Heat Recovery Steam Generators (HRSGs) (1010438), the latest EPRI cycle
chemistry guidelines for operating combined-cycle units with heat recovery steam generators.
Challenges & Objective(s)

Protection requirements are dependent on shutdown requirements. Four types of shutdown are
defined, and users can apply these definitions as appropriate to the units they oversee. Short-term
protection involves keeping the system hot and maintaining condenser vacuum; there is no need
to change water chemistry while these conditions can be maintained. For longer shutdowns, there
are three protection approaches that can be considered: dry protection with warm, dehumidified
air; dry protection with nitrogen; and wet protection with a nitrogen cap.
Applications, Values & Use

The guidelines consider relevant experience from conventional fossil units as well as experience
of combined cycle plant system and component providers and the early experience of
organizations that operate these units. Use of effective protection methods is important in any
generating assets but particularly so in those subjected to peaking service as is often the case
with combined cycle units.
EPRI Perspective
The focal point of the guidelines is the three guiding principles of equipment protection, as
defined in Section 2 of the report. The guiding principles can be used with all suitable operating
chemistries, which should be selected and optimized as outlined in Cycle Chemistry Guidelines
for Combined Cycle/Heat Recovery Steam Generators (HRSGs). The guiding principles for
equipment protection reflect the findings of EPRI research in protecting steam- and water-
touched surfaces in fossil units. By applying these guiding principles and the protection options
outlined in the report’s road map and discussion, users may select and customize shutdown,
layup, and startup practices that will meet the unique needs of their units.
v
Approach
EPRI and EPRI consultants familiar with cycle-chemistry guidelines development and associated
equipment protection requirements and approaches conducted the project. The project team
contacted major suppliers to become familiar with their approaches and also considered the
experience of Program 88 members.
Keywords
Heat recovery steam generator
Chemistry
Shutdown
Layup
Startup
vi
EPRI Proprietary Licensed Material
ABSTRACT
Combined cycle units with heat recovery steam generators offer great flexibility in that they can
be shut down and placed in service very rapidly in comparison to conventional fossil units.
Operating experience has indicated that many of the common causes of component damage and
ensuing availability losses are directly or indirectly related to chemistry practices in use during
shutdowns. The trend in many parts of the world toward increased operation of these assets for
cycling and peaking service is likely to exacerbate the situation.
In many instances, the practices and procedures followed during combined cycle unit operations
are deficient in that they do not provide satisfactory levels of protection to the water and steam
touched components comprising the cycle during shutdown periods. Assessment of the basic
science pertinent to off-line corrosion has resulted in identification of three essential guiding
principles that must be considered when assessing the specific shutdown, layup and startup
requirements of these units. These guidelines are the first of their kind. They introduce the
guiding principles and show operating personnel how they apply during assessment activities for
specific unit characteristics and operating requirements.
vii
ACKNOWLEDGMENTS
The authors of these guidelines
K. Shields, EPRI
B. Dooley, EPRI
A. Aschoff, Consultant
M. Ball, Consultant
Gratefully acknowledge the support and contributions of other members of the EPRI Fossil Plant
Cycle Chemistry Guidelines Team:
A. Bursik, Consultant
D. Swainsbury, Consultant
These individuals reviewed report drafts and provided many useful insights and suggestions.
They were also helpful in ensuring that the report content fitted well with the content of another
report, Cycle Chemistry Guidelines for Combined Cycle/Heat Recovery Steam Generators
(HRSGs). These contributions are especially valuable as it is intended that these guideline reports
be used together to develop optimal cycle chemistry programs customized to meet the needs of
individual combined cycle units.
During preparation of this report, several organizations involved in the provision of combined
cycle plants and/or the manufacture of major components such as heat recovery steam generators
and steam turbines were consulted, as well as two manufacturers of dehumidification equipment.
The following individuals are acknowledged for sharing their views on equipment protection:
M. Arnold, Deltak Cororation

J. Bellows, Siemens Corporation
P. Connin, Bry-Air, Inc.
F. Gabrielli, Alstom Power
G. Rowe, General Electric Company
M. Rziha, Siemens Corporation
J. Schroeder, Nooter/Eriksen
J. Siemasko, Munters Corporation
R. Svoboda, Alstom Power
ix
Valuable insights were also gained from discussions of equipment protection at combined cycle
plants with personnel from member organizations of the EPRI HRSG Dependability Program.
The following individuals are thanked for their contributions to this report:
H. Campbell, Progress Energy

D. Dixon, Lincoln Electric System
P. Pye, SCANA
Special thanks and acknowledgment is extended to Barry Dooley for his many useful
suggestions and words of encouragement as well as his persistent emphasis on keeping the
presentation focused on the unique challenges offered by the wide variety of combined cycle
units comprising the worldwide fleet.
x
CONTENTS
1 INFLUENCE OF SHUTDOWN, LAYUP AND STARTUP PRACTICES ON

COMBINED CYCLE UNIT AVAILABILITY AND RELIABILITY .................................. 1-1
1.1 Cycle Chemistry Management Philosophy.....................................................................1-1
1.1.1 Cycle Chemistry Guidelines for Combined Cycle Units with HRSGs .....................1-1
1.1.2 Chemistry Selection and Optimization....................................................................1-3
1.1.3 Peaking and Cycling Duty ......................................................................................1-3
1.1.4 Protection of the Steam-Water Cycle during Idle Periods to Prevent
Equipment Damage..........................................................................................................1-4
1.2 Effects of Deficient Shutdown, Layup and Startup Practices .........................................1-5
1.2.1 HRSG Tube Damage .............................................................................................1-7
1.2.2 Effects of Shutdown, Layup and Startup on Other Combined Cycle Unit
Components ...................................................................................................................1-10
1.2.2.1 Protection of Steam Turbines .......................................................................1-11
1.3 Chemistry Guidelines for Shutdown, Layup and Startup..............................................1-12
1.3.1 Purpose and Approach.........................................................................................1-12
1.3.2 Guidelines Overview.............................................................................................1-12
1.3.3 How to Use these Guidelines ...............................................................................1-12
1.4 References ...................................................................................................................1-13
2 APPROACH TO GUIDELINES DEVELOPMENT AND CUSTOMIZATION ............. 2-1

2.1 Introduction ....................................................................................................................2-1
2.2 Protection of Water and Steam Touched Surfaces ........................................................2-1
2.2.1 Protection of Steels ................................................................................................2-2
2.2.2 Protection of Copper Alloys ....................................................................................2-6
2.3 Guiding Principles Governing Protection of Cycle Components During Shutdown,
Layup and Startup .................................................................................................................2-6
2.4 Unit Outages and Shutdowns.........................................................................................2-9
2.4.1 Short Term Outage.................................................................................................2-9
2.4.2 Intermediate and Longterm Outages.....................................................................2-10
xi
2.4.3 Extended Outages................................................................................................2-10

2.4.4 Outages Requiring Plant Mothballing Protection..................................................2-10
2.5 Unit Design Factors Influencing Combined Cycle Unit Shutdown, Layup and
Startup.................................................................................................................................2-11
2.5.1 HRSG Tubing and Gas Path Arrangement ..........................................................2-11
2.5.2 Evaporator Circuit Design.....................................................................................2-11
2.5.3 System Drains and Vents .....................................................................................2-11
2.5.4 Materials of Construction......................................................................................2-14
2.5.5 Cycle Chemistry ...................................................................................................2-14
2.5.6 Turbine Bypass Systems......................................................................................2-15
2.5.7 Condensate Polishers and Filters.........................................................................2-15
2.5.8 Condenser Air Removal and Feedwater Deaeration Capabilities ........................2-15
2.6 Application of These Guidelines to Individual Combined Cycle Units ..........................2-15
2.7 References ...................................................................................................................2-16
3 SHUTDOWN AND LAYUP TECHNIQUES FOR WATER AND STEAM

TOUCHED SURFACES OF COMBINED CYCLE PLANT COMPONENTS................ 3-1
3.1 Introduction to Shutdown and Layup of Combined Cycles.............................................3-1
3.1.1 General Layup Considerations ...............................................................................3-2
3.1.2 Shutdown, Layup and Startup of HRSGs with Multiple Evaporator Circuits...........3-3
3.1.3 Feedwater Systems Containing Copper.................................................................3-5
3.2 Roadmap for Selection of Layup Techniques for Use in Combined Cycle Units ...........3-5
3.3 Layup Protection Considerations Using Nitrogen.........................................................3-10
3.3.1 Nitrogen System Design and Operation ...............................................................3-10
3.3.2 Application of Nitrogen .........................................................................................3-12
3.3.3 Plant Maintenance................................................................................................3-12
3.4 Considerations for Dry Layup Protection with Warm, Dehumidified Air .......................3-13
3.4.1 Provision of Dehumidified Air ...............................................................................3-15
3.4.2 Protection in Combined Cycle Plants Using Dehumidified Air..............................3-16
3.4.3 Applications of Protection with Dehumidified Air ..................................................3-17
3.4.3.1 Protection of Steam Turbines and Other Steam Touched Surfaces.............3-17
3.4.3.2 Protection of the Entire Steam-Water Cycle .................................................3-19
3.5 Comparison of Wet and Dry Layup Methods ...............................................................3-21
3.6 Monitoring During Storage ...........................................................................................3-24
3.7 Environmental Considerations .....................................................................................3-24
3.8 References ...................................................................................................................3-25
xii
4 SHUTDOWN FOR VARIOUS CYCLE CHEMISTRIES............................................. 4-1

4.1 Shutdown Requirements for the Various Cycle Chemistries..........................................4-1
4.2 Phosphate Continuum Treatment for Drum HRSG Circuits ...........................................4-2
4.3 All Volatile Treatment for Drum HRSG Circuits..............................................................4-6
4.4 All Volatile Treatment for Once-Through HRSG Circuits ...............................................4-9
4.5 Caustic Treatment for Drum HRSG Circuits.................................................................4-12
4.6 Oxygenated Treatment For Drum HRSG Circuits ........................................................4-15
4.6.1 Shutdown Procedures ..........................................................................................4-16
4.6.2 Short Term Shutdown...........................................................................................4-16
4.6.3 Intermediate, Longterm and Extended Shutdown ................................................4-17
4.6.4 Emergency Shutdown ..........................................................................................4-18
4.6.5 Shutdown as a Result of a Serious Chemistry Excursion ....................................4-18
4.7 Oxygenated Treatment for Once-Through HRSG Circuits...........................................4-19
4.7.1 Shutdown Procedures ..........................................................................................4-19
4.7.2 Short Term Shutdown...........................................................................................4-20
4.7.3 Intermediate, Longterm and Extended Shutdown ................................................4-20
4.7.4 Emergency Shutdown ..........................................................................................4-22
4.7.5 Shutdown as a Result of a Serious Chemistry Excursion ....................................4-22
4.8 References ...................................................................................................................4-22
5 STARTUP FOR VARIOUS CYCLE CHEMISTRIES ................................................. 5-1

5.1 Startup Requirements for the Various Cycle Chemistries ..............................................5-1
5.2 Startup of Units with Phosphate Continuum (PC) Treatment of Drum HRSG
Circuits ..................................................................................................................................5-3
5.3 Startup of Units with All-Volatile Treatment (AVT) of Drum HRSG Circuits ..................5-8
5.4 Startup of Units with All-Volatile Treatment (AVT) of Once-Through HRSG
Circuits ................................................................................................................................5-12
5.5 Caustic Treatment ........................................................................................................5-16
5.6 Startup of Units with Oxygenated Treatment (OT) of Drum HRSG Circuits.................5-20
5.7 Startup of Units with Oxygenated Treatment (OT) of Once-Through HRSG
Circuits ................................................................................................................................5-24
5.8 References ....................................................................................................................5-28
A EQUIPMENT PROTECTION VIA ESTABLISHMENT OF BARRIER FILMS.......... A-1

A.1 Vapor Phase Inhibitors.................................................................................................. A-1
A.2 Filming Amines and Polyamines................................................................................... A-2
A.3 References.................................................................................................................... A-3
xiii
B OXYGEN REMOVAL TECHNIQUES FOR CYCLE MAKEUP WATER.................. B-1

B.1 Vacuum Deaeration ...................................................................................................... B-1
B.2 Catalytic Oxygen Removal............................................................................................ B-3
B.3 Gas Transfer Membrane Systems ................................................................................ B-4
B.3.1 Early GTM Applications Experiences..................................................................... B-5
B.3.2 Use of GTM Systems in Combined Cycle Units..................................................... B-7
B.4 Makeup Water Storage ................................................................................................. B-9
B.5 References.................................................................................................................. B-12
C AIR IN-LEAKAGE MONITORING AND CONTROL................................................ C-1

C.1 Cycle Air In-Leakage .................................................................................................... C-1
C.2 Rotameters ................................................................................................................... C-1
C.3 Multisensor Probe......................................................................................................... C-2
C.4 Air In-Leakage Source Identification Methods .............................................................. C-6
C.4.1 Inert Gas Methods ................................................................................................ C-6
C.4.2 Ultrasonic and Infrared Techniques for Air In-leakage Detection .......................... C-7
C.5 Fossil Plant Air In-Leakage Management Strategies.................................................... C-7
C.5.1 Leak Detection Using Helium................................................................................ C-7
C.5.2 Leak Detection Using Sulfur Hexafluoride ............................................................ C-9
C.5.3 Use of Multisensor Probe System....................................................................... C-11
C.6 References ................................................................................................................. C-12
xiv
LIST OF FIGURES
Figure 1-1 Possible Effects of Deficient Shutdown, Layup and Startup Practices in
Combined Cycle Units........................................................................................................1-6
(7)
Figure 1-2 Pitting in HRSG Evaporator Tube .........................................................................1-8
(7)
Figure 1-3 HRSG Economizer Tube Fin Damage Caused by Acid Dewpoint Corrosion ........1-8
Figure 1-4 Examples of Underdeposit Corrosion Damage: (a) HRSG HP Evaporator
Tube with Hydrogen Damage; (b) Conventional Boiler Waterwall Tube with
Deposits Removed to Show Caustic Corrosion Damage; (c) HRSG HP Evaporator
(7)
Tube with Acid Phosphate Corrosion Damage ................................................................1-9
(7)
Figure 1-5 Flow-accelerated Corrosion Damage in Low Pressure Evaporator Tube ...........1-10
Figure 1-6 Schematic Showing Influence of Turbine Operation and Shutdown on
(13)
Corrosion Fatigue and Stress Corrosion Cracking ........................................................1-11
Figure 2-1 Cross Section through a Pit Showing Corrosion Product Cap and Corrosion
Products in the Pit ..............................................................................................................2-3
Figure 2-2 Schematic Outlining Various Stages of Pit Nucleation According to the Point
Defect Model Source: Reference 9 ...................................................................................2-5
(2)
Figure 2-3 Natural Circulation, Vertical Tubed, Multi-pressure HRSG ...................................2-12
(2)
Figure 2-4 Horizontal Tube Typical Configuration for Drum-type HRSG ...............................2-13
Figure 3-1 Road Map for Shutdown and Layup Guidelines Common to Most Combined
Cycle Units .........................................................................................................................3-6
Figure 3-2 Corrosion Rate of Steel Relative to Humidity of Air ................................................3-14
(5,9)
Figure 3-3 Rotary Desiccant Dehumidifier ...........................................................................3-15
Figure 3-4 Dry Layup of 107 MW Turbine Showing Measured Values of Temperature
and Air Humidity...............................................................................................................3-18
Figure 3-5 Turbine: Dry Layup Using Dehumidified Air ...........................................................3-19
Figure 3-6 Protection of the Entire Steam-Water Cycle with Dehumidified Air ........................3-20
Figure 4-1 Road Map for Shutdown of Combined Cycle Units with Drum Type
Evaporator HRSG Circuits Using Phosphate Continuum (PC) Chemistry .........................4-3
Evaporator HRSG Circuits using All Volatile Treatment (AVT) ..........................................4-7
Figure 4-3 Road Map for Shutdown of Combined Cycle Units with Once-Through
Evaporator HRSG Circuits using All Volatile Treatment (AVT) ........................................4-10
Evaporator HRSG Circuits using Caustic Treatment (CT) ...............................................4-13
Figure 4-5 Shutdown Chemistry Guidance for Drum Type Evaporator Circuits using OT
Chemistry: Short Term Shutdowns ..................................................................................4-17
xv
Figure 4-6 Shutdown Chemistry Guidance for Drum Type Evaporator Circuits using OT
Chemistry: Intermediate, Longterm and Extended Shutdowns ........................................4-18
Figure 4-7 Shutdown Chemistry Guidance for Once-Through Evaporator Circuits using
OT Chemistry: Short Term Shutdowns ............................................................................4-20
Figure 4-8 Shutdown Chemistry Guidance for Once-Through Evaporator Circuits using
OT Chemistry: Intermediate, Longterm and Extended Shutdowns ..................................4-21
Figure 5-1 Road Map for Startup of Combined Cycle Units with Drum Type Evaporator
HRSG Circuits Treated With Phosphate Continuum (PC) Chemistry ................................5-6
HRSG Circuits Treated All Volatile Treatment (AVT) Chemistry......................................5-10
Figure 5-3 Road Map for Startup of Combined Cycle Units with Once-Through
Evaporator HRSG Circuits Treated All Volatile Treatment (AVT) Chemistry ...................5-14
HRSG Circuits Treated With Caustic Treatment (CT) Chemistry.....................................5-18
Figure 5-5 Road Map for Startup and OT Conversion of Combined Cycle Units with
Drum Type Evaporator HRSG Circuits Treated With Oxygenated Treatment (OT)
Chemistry .........................................................................................................................5-22
Figure 5-6 Road Map for Startup of Combined Cycle Units with Once-through
Evaporator HRSG Circuits Treated with Oxygenated Treatment (OT) Chemistry ...........5-26
Figure B-1 Vacuum Degasifier................................................................................................ B-2
Figure B-2 Components of a GTM Unit .................................................................................. B-4
Figure B-3 GTM System Process Flow Diagram (Note: 1 gal = 3.785 litres).......................... B-6
Figure B-4 GTM System Process Flow Diagram (Note: 1 gal = 3.785 liters).......................... B-6
(15)
Figure B-5 A Storage Tank Nitrogen System and Sparging Elements .............................. B-11
Figure C-1 Multisensor Probe (courtesy of Intek, Inc) ............................................................ C-3
Figure C-2 Validating Arrangement Multisensor Probe Instrument Schematic........................ C-4
Figure C-3 Flow Schematic for SF6 Analyzer System ........................................................... C-10
Figure C-4 Schematic Diagram of SF6 Sampling System ..................................................... C-11
xvi
LIST OF TABLES
Table 3-1 Shutdown and Layup Advantages and Disadvantages: Wet Layup ........................3-22
Table 3-2 Shutdown and Layup Advantages and Disadvantages: Nitrogen Blanketing ..........3-22
Table 3-3 Shutdown and Layup Advantages and Disadvantages: Dehumidified Air ...............3-23
Table C-1 Summary of Parameters Determined with the Multisensor Probe System ............. C-2
Table C-2 Examples of a Three-Probe Air In-leakage Measurement System (1 scfm =
3
1.7sm /h) ........................................................................................................................... C-5
Table C-3 Some Examples of Observed RheoVac Monitor Measured Data and
Corresponding Identification of Leak Presence and Leak Location Determinations
3
(1 scfm = 1.7 sm /h) .......................................................................................................... C-5
xvii
1
INFLUENCE OF SHUTDOWN, LAYUP AND STARTUP
PRACTICES ON COMBINED CYCLE UNIT
AVAILABILITY AND RELIABILITY
1.1 Cycle Chemistry Management Philosophy
Meeting operational water chemistry requirements in conventional fossil plant cycles is generally
recognized as a key part of ensuring satisfactory levels of unit availability and reliability.
Further, it has been observed that deterioration of equipment performance occurs when the
chemistry is not optimized. In recognition of the influence of cycle chemistry on the unit,
considerable effort has been expended to establish operating cycle chemistry guidelines. Many
organizations have successfully implemented these guidelines.(1-3) Subsequent chemistry
program benchmarking, EPRI Cycle Chemistry Improvement Program Workshops and
chemistry value assessment activities have all demonstrated the benefits of applying and
following the guidelines.
Many of the benefits possible with effective chemistry programs for feedwater and boiler water
during normal operation may be diminished in the absence of effective chemistry control during
idle periods. In many cases little or no attention is given to protection of equipment while the
unit is out of service. Establishment of the optimum chemistry under all conditions has been an
integral part of EPRI’s philosophy for management of cycle chemistry in fossil units. A
guideline dedicated to cycling, startup, shutdown and layup was published in 1998.(4)
This early work concentrated on fossil cycles with conventional boilers. The emergence of a
worldwide fleet of combined cycle units with heat recovery steam generators (HRSGs)
represented a significant change in design and operation relative to conventional units.
Chemistry management philosophies and guidelines developed for conventional plant cycles are
not entirely applicable to combined cycle units, the features and characteristics of which offer
unique challenges to operators and chemists.
1.1.1 Cycle Chemistry Guidelines for Combined Cycle Units with HRSGs
Interim cycle chemistry guidelines for combined cycles with HRSGs were introduced by EPRI in
1998.(5) as the initial product developed as part of EPRI efforts to establish the HRSG
Dependability Program. Work on the first revision of these guidelines was initiated in 2004 with
the final report issued in 2005.(6)
1-1
Influence of Shutdown, Layup and Startup Practices on Combined Cycle Unit Availability and Reliability
The 1998 interim guidelines focused primarily on operational cycle chemistry needs; they
considered the science on which guidelines for conventional cycles were based and unique
characteristics and requirements of combined cycle units. They were developed to address a
multiplicity of chemistry related failures and damage incidents that were being reported by
combined cycle plant personnel; these include:
• Evaporator carryover and steam turbine damage
• Several types of HRSG tube failures (HTF)
– Flow-accelerated corrosion (FAC) damage in feedwater systems, economizers and low
pressure (LP) evaporators
– Underdeposit corrosion in high pressure (HP) evaporator tubing by three mechanisms
(hydrogen damage, acid phosphate corrosion and caustic corrosion)
– Corrosion fatigue
• Corrosion during HRSG shutdown and idle periods
Investigation and evaluation of these early events concentrated on damage to steam turbines and
HRSG tube failures since such events will have the greatest impacts on unit availability. In the
case of evaporator carryover and turbine damage, it was found that several factors could be
involved. HRSG design and operating practices were often deficient, resulting in episodes of
carryover and transport of contaminants to the steam turbine. In many instances, the unit did not
include the instrumentation needed to allow early detection of carryover problems. Performance
testing of steam purity and related unit commissioning activities were apparently not able to
identify conditions that could lead to future problems in all cases. In developing the interim
chemistry guidelines for combined cycle plants, these incidents underscored the need for proper
selection of the chemistry for feedwater and individual evaporator circuits, as well as the
importance of steam drum mechanical carryover as a chemistry monitoring parameter. These
aspects have been given far greater emphasis in the latest revision of the cycle chemistry
guidelines.(6)
EPRI investigations of numerous HRSG tube failure incidents in various combined cycle unit
configurations confirmed that many of the tube failure mechanisms are essentially identical to
those observed in boilers of conventional cycles. However, responsible root causes and suitable
corrective actions for HRSG tube failures by these otherwise common mechanisms may deviate
from the experience with these mechanisms in conventional boilers. To address these
deficiencies as well as address tube failure mechanisms unique to HRSGs, a tube failure manual
was developed and published in 2002.(7) It was also determined that many HRSG tube failures
resulted from deficient designs and that avoidance of such failures would thus be possible in
future units. These findings were presented in a report that addressed important aspects of
ensuring reliable HRSG delivery.(8)
Initially, less emphasis was placed on corrosion during HRSG shutdown and idle periods, since
steam turbine damage and operational HRSG tube failure problems were of greater immediate
concern. Also, prior to increases in fuel prices in many markets, it was not unusual for combined
cycle units to operate under longterm power supply contracts. Thus it was quite common to
1-2
operate many if not most combined cycle units for extended periods with minimal shutdowns for
purposes of economy.
The interim cycle chemistry guidelines for combined cycle plants with HRSGs included a
section on shutdown and layup considerations that reviewed the techniques and procedures
generally regarded as appropriate for conventional fossil plant units.(5) Past and present
equipment protection practices available for combined cycle units are quite consistent with those
developed for use in conventional units. The authors of these revised guidelines assessed
industry practices and confirmed that there has been very little innovation on the part of
equipment manufacturers and operators in this regard. It was also determined that there is
considerable interest in establishment of equipment protection techniques that would offer
operators more flexibility than the traditional methods.
1.1.2 Chemistry Selection and Optimization
Many chemistry related problems in conventional fossil units relate to improper selection of
feedwater and boiler water chemistry. In some instances, incorrect choices were made initially,
while in other, the significance of changes in unit design and operation on choice of chemistry
were not recognized. The latest EPRI chemistry guidelines for conventional plants(1-3) provide
clear direction in chemistry selection and stress the importance of periodic reassessment of the
changing needs of the unit.
A similar approach is needed in combined cycle units and this is one of many improvements
incorporated within the first revision of the cycle chemistry guidelines for combined cycle units
with HRSGs.(6) Such efforts will be most effective in combined cycle unit designs that properly
consider the operational chemistry requirements(8) and in units that evaluate the chemistry
transients to avoid damage during the commissioning period and early operations.(9)
Complete optimization of the chemistry requires more than proper initial selection and periodic
reassessments of the operating feedwater and evaporator water treatments. It requires that the
chemistry environment be considered with provisions made to ensure that it is monitored and
controlled as needed. This is often overlooked or neglected during idle periods such as
maintenance shutdowns, when attention is normally directed to other important outage activities
such as repairs, testing and inspections. Depending on the specific work to be done, some
compromises in equipment layup may be needed. Unfortunately, it is also very common to
provide unsatisfactory protection of the equipment during economy outages when no work needs
to be done but uncertainties with respect to the duration of the shutdown period or the time
required to return the unit to service may exist.
1.1.3 Peaking and Cycling Duty
For reasons of economy, it may be necessary to operate many combined cycle units in the
peaking mode and/or subject to load cycling when in service. Many of the early high pressure
designs assumed that the units would be operated primarily under essentially baseload
conditions. The most serious consequence of this has been the high incidence of fatigue type
1-3
failures, due to more frequent thermal transients. (8, 9) Additional consequences relate to the fact
that the cycle chemistry is more difficult to maintain, especially if it was not selected properly
initially. Thus corrosion protection during shutdown and startup may not be adequate; deficient
layup practices can further compound the problem.
1.1.4 Protection of the Steam-Water Cycle during Idle Periods to Prevent

Equipment Damage
The protective oxide layers formed on water and steam touched surfaces during normal service
operation cannot be maintained during idle periods unless appropriate steps are taken to control
the chemistry environment. Unfortunately, chemistry control during shutdown periods is not
always consistent with those practices known to protect steam generator tube waterside and
steamside surfaces and surfaces of other combined cycle components from corrosion. Deficient
chemistry practices during unit shutdown, layup and startup are either directly responsible for or
a contributing factor to many HRSG waterside tube damage and failure mechanisms. Further,
such deficient practices may have negative impacts on unit performance. Other non-chemical
aspects of fossil unit shutdown and startup are also important as these can have influence on
some HRSG tubing damage mechanisms, most notably thermal fatigue, irrespective of the
chemistry practices followed.
Current industry practices with respect to protection of fossil units were captured as part of a
survey of the worldwide community of water chemistry specialists, as part of a survey on cycle
chemistry in fossil generating units conducted in 2003.(10) In conventional fossil plants, survey
participants indicated that:
• Only 45% nitrogen blanket boilers during shutdowns
• Only 18% provide protection to reheaters during shutdowns
• Only 12% provide protection to steam turbines during long outages
• Only 11% nitrogen blanket feedwater heaters during shutdown
Although clearly far from desirable, these figures on equipment protection actually represent a
slight improvement over results of earlier surveys of fossil plant chemistry personnel on this
subject.
When asked to indicate their most serious cycle and chemistry problems, survey participants
often indicated concerns which either typically or at least may in some instances involve the
chemistry environment maintained during idle periods as well as operational cycle chemistry
surveillance and control. These include:
• Turbine Deposits-Copper and Other (23%)
• Boiler Tube Failures by Corrosion Fatigue (22%)
• Boiler Tube Failures by Hydrogen Damage (14%)
• Feedwater Heater Corrosion and Transport (15%)
1-4
• Iron and Copper (12%)

• Condenser Leaks (49%)
These results fall far short of the EPRI cycle chemistry program goal stating that the cycle
chemistry will be effectively managed and optimized under all operating conditions. When
considering these statistics it quickly becomes clear that nearly every cycle component in contact
with water and steam can be affected if satisfactory protection is not available. Furthermore,
most of the organizations involved in the survey were not giving their generating assets the off-
line protection needed to maximize their performance.
Although this survey included conventional fossil units, many of the responding organizations
also operate combined cycle units with HRSGs. In view of this, there is reason for concern that
many combined cycle units may ultimately exhibit a similar pattern. This concern is particularly
acute in the case of units initially designed for baseload operation that now operate as peaking
and cycling units due to present day economics governing dispatch of generating units. The
HRSGs in these units are often subject to thermo-mechanical fatigue damage and may not have
the facilities needed to support frequent shutdown/layup/startup requirements. In recognition of
the importance of establishing combined cycle unit designs that facilitate operating practices and
design features that support protection of the equipment during shutdowns EPRI developed the
previously mentioned publication that focused on delivery of high reliability HRSGs.(8)
1.2 Effects of Deficient Shutdown, Layup and Startup Practices
The acts of removing a unit from service, maintaining it idle for various time periods and
returning it to operation produce substantial chemical and thermal transients, which are
potentially detrimental to the HRSG and other components of the steam-water cycle. Figure 1-1
identifies some possible consequences of deficient control of the chemistry at these times.
As with the operational chemistry, the chemistry during shutdown and layup must be effective in
prevention of contaminant ingress and transport and of corrosion product formation and transport
to areas where deposition will occur. In addition to contamination by dissolved solids and gases
such as oxygen and carbon dioxide, outages represent a situation where other contaminants may
be introduced to the cycle as a consequence of maintenance and inspection activities. Examples
include grit blast media and other abrasives, paints, solvents and preservatives, cleaning
chemicals, ambient dust and dirt, etc. It should be self-evident that during every outage where the
steam-water cycle components will be opened that it is essential to have good accountability for
materials and their usage and to practice good housekeeping practices. Also, making a final
examination and, if needed, removal of foreign material prior to filling equipment with water for
startup is very desirable as it can save much more time than it requires.
1-5
Figure 1-1
Possible Effects of Deficient Shutdown, Layup and Startup Practices in Combined Cycle
Units
The effect most commonly experienced is loss of the protective oxide structure formed on water
and steam touched surfaces during normal operation, pitting and general corrosion of
unprotected surfaces during the idle period, and transport of metal oxides into the HRSG during
the ensuing startup. Condenser air removal and thermal deaerator performance are often deficient
during shutdown and startup periods, and these systems normally represent points of air (and
oxygen) ingress while the unit is idle. Failure to exclude air during the shutdown often serves to
minimize the effectiveness of protective layup measures.
The makeup water supply is often saturated with dissolved oxygen and carbon dioxide. While
this is not optimal for normal service operation, it is unaccetptable as fill water for startup of
equipment. Starting the unit up with oxygen saturated water invites further corrosion and
subsequent oxide transport. In cases where the water supply is saturated with oxygen or is
exposed to air (and oxygen) while in storage, improvements are desirable to remove oxygen
prior to introducing it to the unit.
Startup operations must avoid chemistry excursions related to improper chemical dosing,
condensate polisher (where available) operations and HRSG blowdown. Care must be taken to
avoid steam contamination by means of excessive spray attemperation or carryover from drum
type evaporator circuits. Drum level surveillance and control is especially important to avoid
mechanical carryover of boiler water with saturated steam during startup. Sampling systems and
on-line analyzers should be placed in service as soon as possible to allow timely identification of
contamination during the startup.
1-6
1.2.1 HRSG Tube Damage
In 2002, EPRI completed the first and only comprehensive assessment of all aspects of tube
failures in the HRSGs.(7) Damage mechanisms active in HRSGs are often analogous to those
experienced in conventional boiler tubing; however there are frequently important differences in
the underlying root causes, which will require unique corrective actions.
Discussion of the individual tube failure mechanisms of Reference 7 indicates that deficient
shutdown, layup and startup practices may be involved.(7, 11) Three chemistry related
mechanisms are very likely to be active or become active in the future in HRSGs if the unit
shutdown, layup and startup practices are deficient:(7)
• Pitting, Figure 1-2
• Acid Dew Point Corrosion, Figure 1-3
• Corrosion Fatigue
Pitting attack will occur at surfaces exposed to moisture and oxygen under stagnant conditions.
Proper layup protection of idle units prevents pitting. Acid dew point corrosion is influenced by
the fireside environment and metal temperatures; corrosion may be exacerbated during steam
generator shutdown. Corrosion fatigue is a complex mechanism, with both environmental and
mechanical influences. It is active during all operating modes. Proper layup is crucial since
breakdown of the protective oxide layer as a result of pitting during unprotected shutdown
influences the mechanism.
The following underdeposit mechanisms are active entirely or at least mainly during normal
HRSG operation, mainly in high pressure evaporator circuits.
• Hydrogen Damage, Figure 1-4(a)
• Caustic Corrosion, Figure 1-4(b)
• Acid Phosphate Corrosion, Figure 1-4(c)
Hydrogen damage, acid phosphate corrosion and caustic corrosion cause failures in drum type
evaporators. These mechanisms are influenced by shutdown, layup and startup practices in that
they either require or are enhanced by accumulation of waterside deposit materials. Deposit
material is transported to the steam generator with the feedwater; transport is most significant
during startups, especially when cycle equipment has not been protected during the outage.
In the case of designs where water from the low pressure (LP) or intermediate pressure (IP) is
used as supply to the high pressure (HP) circuit, flow-accelerated corrosion (FAC) represents
another source of iron oxide (Figure 1-5). Proper selection of the cycle chemistry essentially
eliminates single phase FAC and may reduce the extent of two-phase FAC. For optimal control
of FAC, it is important to maintain the same chemistry environment (oxidizing) at all times. A
commonly observed deficient protection practice involves addition of wet layup treatments
(reducing agents) that alter the chemical environment and will not provide optimal resistance to
FAC.
1-7
Figure 1-2
Pitting in HRSG Evaporator Tube (7)
Figure 1-3
HRSG Economizer Tube Fin Damage Caused by Acid Dewpoint Corrosion (7)
1-8
(a) (b)
(c)
Figure 1-4
Examples of Underdeposit Corrosion Damage: (a) HRSG HP Evaporator Tube with
Hydrogen Damage; (b) Conventional Boiler Waterwall Tube with Deposits Removed to
Show Caustic Corrosion Damage; (c) HRSG HP Evaporator Tube with Acid Phosphate
Corrosion Damage(7)
1-9
Figure 1-5
Flow-accelerated Corrosion Damage in Low Pressure Evaporator Tube (7)
1.2.2 Effects of Shutdown, Layup and Startup on Other Combined Cycle Unit
Components
The increased likelihood of future HRSG tube failures are but one possible consequence of
deficient shutdown, layup and startup practices. However, such deficient practices can affect
other equipment in the cycle. Possible detrimental effects include:
• Pitting and general surface corrosion of water and steam touched surfaces in condensers,
external deaerators, headers and piping, and steam turbines
• Deposition of corrosion products on evaporator feed pumps, in feedwater preheaters, in
evaporator economizer and waterwall tubing, in once-through evaporator circuit orifices, in
blowdown systems and on steam turbines
• Corrosion of the turbine in the presence of moisture, oxygen and salt deposits; such damage
is often a precursor to future corrosion fatigue and stress corrosion cracking failures
• Exfoliation of steam path oxides resulting in solid particle erosion of steam turbines
• Hideout and return of impurities and treatment chemicals
• Increased thermal stresses, strain, and vibration
• Contamination of the steam-water cycle by equipment and material used during maintenance
activity
1-10
Most of these concerns can be ameliorated through the same sort of diligence needed during unit
shutdown, layup and startup periods to minimize the risk of HRSG tube damage. In fact, it is
now clear that the most effective protection strategies are those that address the entire steam-
water cycle. Perhaps the best example of this is the feedwater corrosion products that enter the
HRSG and form deposits on evaporator tube waterside surfaces. These deposits increase the risk
of on-line underdeposit corrosion (by hydrogen damage, acid phosphate corrosion or caustic
gouging), shorten the interval between chemical cleans, and possibly reduce cycle efficiency.
1.2.2.1 Protection of Steam Turbines
It was indicated earlier that carryover to the steam turbine has been experienced during the
commissioning and early commercial operation of many combined cycle units with HRSGs.
Research investigations of stress corrosion cracking (SCC) and corrosion fatigue (CF) in steam
turbines have determined that damage by these mechanisms typically initiates at micro-pits in the
passive surface layer formed while the turbine is in service. During unprotected outages, pitting
attack can break down this protective surface oxide layer. A schematic representation of the
influences of turbine operation and turbine shutdown is shown in Figure 1-6. A deterministic
model is being developed by EPRI to define the conditions leading to damage by these
mechanisms more precisely. Pit growth and onset of SCC or CF are dependent on operating
conditions; however, these mechanisms cannot become active if the requisite precursor
conditions associated with unprotected shutdowns are avoided. The latest research clearly
suggests that protection of steam turbines during all outages is essential to avoiding the
developments of micro-pits that are the precursors to cracking via SCC and CF.(13, 14) Field
experience has shown that use of dehumidified air is an effective means of preventing
accumulation of moisture and/or liquids on turbine surfaces during the shutdown and layup
periods. Following this approach reduces the risk of developing pitting, corrosion fatigue and
stress corrosion cracking in turbine disks and blades.
Figure 1-6
Schematic Showing Influence of Turbine Operation and Shutdown on Corrosion Fatigue
and Stress Corrosion Cracking(13)
1-11
1.3 Chemistry Guidelines for Shutdown, Layup and Startup
1.3.1 Purpose and Approach
The primary purpose of these guidelines is to make operators of combined cycle plants aware of
the importance of protecting cycle water and steam touched surfaces of plant components during
idle periods and of available and effective techniques and practices that can support equipment
protection. The approach taken is to establish guiding principles applicable to all cycle designs,
treatment approaches and operational requirements. Suitable methods consistent with these
guiding principles for protection of combined cycle units are identified and discussed. Road
maps are introduced to enable operators to evaluate and select suitable approaches consistent
with the guiding principles and specific unit characteristics. Determination of the specific
optimal requirements for implementing effective protection of individual units is beyond the
scope of these guidelines; users must perform such assessments and initiate the correct actions,
including engineering of solutions, on a case by case basis. This process includes monitoring to
evaluate the efficacy of the protection practices in use.
1.3.2 Guidelines Overview
Subsequent sections of this guidelines document focus on specific aspects of off-line protection
of steam and water touched surfaces of combined cycle units. Section 2 presents background
information on corrosion damage in unprotected equipment and establishes the guiding
principles that must be adhered to in order to prevent such damage. Section 2 also identifies and
discusses important factors that operators of combined cycle units must consider when
evaluating equipment protection needs, and developing implementation strategies. General
considerations of unit shutdown and protection methods are presented in Section 3, along with an
overall road map illustrating the approach to be followed. Shutdown considerations specific to
the various evaporator water chemistries are discussed in Section 4. Return of combined cycle
units to service following shutdowns is the subject of Section 5; discussion of the startup is based
on chemistry-specific concerns for each of the evaporator treatment options available.
1.3.3 How to Use these Guidelines
These guidelines are intended to be used in combination with properly selected and optimized
feedwater and evaporator water treatments, which are described in a separate EPRI document,
Cycle Chemistry Guidelines for Combined Cycle Heat Recovery Steam Generators (HRSG),
Revision 1.(6) Users desiring to evaluate their shutdown, layup and startup practices should first
ensure that the chemistry in use has been properly selected and optimized. The user should then
consider the guiding principles for equipment protection and consider current and anticipated
future unit operating requirements, outage characteristics and unit design aspects, as addressed in
Section 2. Within this framework, the guidelines of Sections 3 through 5 may be reviewed to
determine suitable approaches based on the guiding principles that may be further customized as
needed for effective chemistry control during combined cycle unit shutdown, layup and startup.
1-12
Additional information is included in three report appendices. Appendix A discussed some

alternative equipment protection approaches which rely on establishment of barrier films on the
surfaces to be protected. Appendix B discusses options for removal of dissolved oxygen from
cycle makeup water. Measurement and control of cycle air inleakage during startup and normal
operation is the subject of Appendix C.
1.4 References
1. Cycle Chemistry Guidelines for Fossil Plants: All-volatile Treatment, Revision 1. EPRI, Palo
Alto, CA: 2002. 1004187.
2. Cycle Chemistry Guidelines for Fossil Plants: Phosphate Continuum and Caustic Treatment.
EPRI, Palo Alto, CA: 2004. 1004188.
3. Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment. EPRI, Palo Alto, CA:
2005. 1004925.
4. Cycling, Startup, Shutdown and Lay-up Fossil Plant Cycle Chemistry Guidelines for
Operators and Chemists. EPRI, Palo Alto, CA: 1998. TR-107754.
5. Interim Cycle Chemistry Guidelines for Combined Cycle Heat Recovery Steam Generators
(HRSGs). EPRI, Palo Alto, CA: 1998. TR-110051.
6. Cycle Chemistry Guidelines for Combined Cycle/Heat Recovery Steam Generators
(HRSGs). EPRI, Palo Alto, CA: 2006. 1010438.
7. Heat Recovery Steam Generator Tube Failure Manual. EPRI, Palo Alto, CA: 2002. 1004503.
8. Delivering High Reliability HRSGs. EPRI, Palo Alto, CA: 2003. 1004240.
9. Diagnostic/Troubleshooting Monitoring to Identify Damaging Cycle Chemistry or Thermal
Transients in Heat Recovery Steam Generator Pressure Parts. EPRI, Palo Alto, CA: 2005.
1008088.
10. Survey Results, Proceedings: Seventh International Conference on Cycle Chemistry in Fossil
Plants: June 3-5, 2003, Houston, Texas. EPRI, Palo Alto, CA: 2004. 1009194.
11. K. J. Shields and A. F. Aschoff, “Influence of Steam Generator Shutdown, Layup and Startup
Chemistry Control Practices on Steam Generator Tube Failures”, Proceedings: Boiler Tube
and HRSG Tube Failure and Inspection International Conference: November 2-4, 2004, San
Diego, California. EPRI, Palo Alto, CA: 2004. (Publication pending.)
12. Heat Recovery Steam Generator (HRSG) Chemical Cleaning Guidelines. EPRI, Palo Alto,
CA: 2003. 1004499.
13. Corrosion of Low Pressure Steam Turbine Components. EPRI, Palo Alto, CA: 2000.
1000557.
14. Development of Code to Predict Stress Corrosion Cracking and Corrosion Fatigue of Low
Pressure Turbine Components. EPRI, Palo Alto, CA: 2004. 1004190
1-13
2
APPROACH TO GUIDELINES DEVELOPMENT AND
CUSTOMIZATION
2.1 Introduction
Effective protection of steam and water touched components of fossil plant cycles must consider
the relevant science (Section 2.2). Further, protection strategies must be validated by successful
field operating experience. Guiding principles for equipment protection are outlined in Section
2.3. Conformance with the guiding principles is considered essential when evaluating, selecting
and applying the available choices proven effective for equipment protection, as covered in
Section 3. Sections 4 and 5 present chemistry-specific concerns for start-up of heat recovery
steam generators (HRSGs) with the various evaporator design and chemical treatment
combinations.
Experience has shown that a number of equipment protection strategies exist, consistent with the
guiding principles, that are effective for equipment protection in conventional fossil plant cycles
and thus considered suitable for use in combined cycle units. These strategies are discussed in
detail in Section 3. Applicability of established equipment protection measures and selection of
the optimal approach is dependent on many factors. These include the type of outage (Section
2.4) and other factors specific to the unit (Section 2.5). The need to customize the guidelines for
optimal use in individual combined cycle units is discussed in Section 2.6.
Two methods of equipment protection of possible interest, mainly for extended protection based
on establishment of barrier films on surfaces, are identified and briefly discussed in Section 2.7;
further information is included in Appendix A.
2.2 Protection of Water and Steam Touched Surfaces
Upon determining that a combined cycle unit is to be removed from service, the chemistry
environment within the steam-water cycle must be considered and adjusted as needed to ensure
suitable protection of all steam and water touched surfaces until such time as the unit is back in
service. Different approaches exist and may be suitable depending on local conditions and unit
operational requirements. Irrespective of these issues the applicable science that influences
equipment protection are the same.(1) Thus the unit must be removed from service, placed in a
protective layup condition that supports return of the unit to service with minimal impact on
water chemistry and the condition of surface oxides formed during normal unit operations. The
transitions between periods of operation must provide adequate protection under all conditions
that may be encountered until the unit is restored to service. From a cycle chemistry perspective,
2-1
Approach to Guidelines Development and Customization
passage through such transitions should be approached as a seamless, continual process, as

opposed to discrete steps. For example, a layup procedure that allows ingress of ambient air prior
to implementation is likely to be very ineffective relative to a procedure that minimizes such
ingress under all operating conditions.
Simply stated, the purpose of layup is to protect the steam and water touched surfaces of
equipment comprising the steam-water circuit from corrosion while the combined cycle unit is
not generating power. Corrosion may take the form of pitting attack or as the more widespread
breakdown of the protective metal oxide surface layer formed during service.
Materials of construction influence the feedwater chemistry selection as well as the approach to
layup. In combined cycle units, the vast majority of surfaces comprising the steam-water cycle
are comprised of ferrous materials. Based largely on unfavorable experience in conventional
plant cycles and changes in the relative cost of materials over time, most combined cycle units
include little or no copper based materials in water and steam touched components. The tubing of
water cooled surface condensers is a possible exception but even here, materials such as stainless
steels or titanium are usually the preferred choice.
2.2.1 Protection of Steels
In normal service with proper chemistry conditions, a protective oxide layer is formed on steel
surfaces in contact with water and steam. Disruption of the protective oxide layer will occur
during unprotected shutdowns. Corrosion will occur when surfaces are in contact with moisture
or stagnant water that contains dissolved oxygen. Thus when wetted surfaces are to be
maintained wet, it is crucial to both exclude oxygen ingress and avoid stagnant conditions.
It is quite common for some water to be retained following draining of plant equipment.
Condensation of moisture on previously dry surfaces as a consequence of typical ambient air
temperature and humidity variations will occur under most climate conditions. Retained water on
surfaces and surface moisture formed as consequence of normal condensation can lead to attack
on the protective surface oxide when in contact with ambient air, which serves as a source of
oxygen.
Stagnancy should be regarded as a prerequisite condition for the inception of pitting in steels at
wetted surfaces when oxygen is present. Thus the protection of steel surfaces during shutdown
requires that either: (1) contact with moisture and water is avoided or (2) wetted surfaces are
denied access to oxygen in air and the water is circulated to avoid stagnant conditions.
Pitting of metals is a complex subject. The phenomenon of attack on steels in aerated stagnant
water is common to many industries and well understood. Features of pitting damage on steels
are quite distinct.(2) For example, pits can either be numerous and closely spaced, or isolated.
They are often covered with caps of corrosion products. An example of pitting in an HRSG
evaporator tube is provided in Figure 1-2. The pits are typically filled with corrosion products,
particularly red hematite iron oxide (Fe2O3) which is the thermodynamically favored reaction
product of iron with oxygen under conditions of high oxygen activity. This form of pitting may
undercut the surface.
2-2
Figure 2-1 displays a cross-sectional view through an oxygen pit that was filled with corrosion
products and covered by a distinctive corrosion cap.
Figure 2-1
Cross Section through a Pit Showing Corrosion Product Cap and Corrosion Products in
the Pit
Experience in HRSG units has documented the development of pitting damage. Affected
locations include feedwater heaters and preheaters, economizers, and evaporators. However,
superheaters and reheaters are also viewed as susceptible to pitting damage. Horizontal tubing is
particularly vulnerable to pitting if not fully drainable and not provided with a protective
environment during the shutdown periods. Other component surfaces, particularly those
composed of carbon steel are susceptible to pitting attack if proper shutdown and layup practices
are not used.(2)
Pitting corrosion can produce damage and failures in a variety of components, materials and
aqueous environments. Pitting is considered a likely precursor to other damage mechanisms
including corrosion fatigue and stress corrosion cracking. Accordingly, it has been the subject of
extensive research and development. As a result of these activities, the complex nature of the
pitting process has become well understood. Various modeling studies, in combination with
other research, have helped to determine how pits develop and identified the important
environmental parameters that influence the mechanism.
It cannot be overemphasized that the key feature to note is that pitting only occurs during
unprotected shutdown periods, and not when the unit is operating. During shutdown, the
remaining water is often left stagnant and steel surfaces left open to the atmosphere. Under these
conditions, the residual water (or moisture condensing on surfaces) becomes saturated with
oxygen.
Pitting and other related localized corrosion processes such as crevice corrosion involve selective
breakdown of the passive films normally present on the metal surface. The environment will
affect pitting activity and severity. Chloride ions, for instance, are well known for causing
chemically induced breakdown of the passive layer, which results in pitting corrosion. As an
2-3
example, improper chemical cleaning with hydrochloric acid often results in severe pitting
attack. However, impurities such as chloride, if present in the water can also exacerbate pitting
damage during unprotected shutdowns.
Other anions besides chloride have been determined to be capable of attacking the passive film.
For example, dilute sulfate solutions can lead to pitting in reheaters and in the low pressure
section of steam turbines of conventional fossil units. These pits exhibit distinct differences from
pitting which can develop in relatively pure water normally present in the steam-water cycle
during shutdowns.(2)
The pitting corrosion process can be considered to consist of two stages: pit induction (i.e., the
time to first pit formation, also termed “initiation” or “nucleation”) and subsequent growth. Pits
tend to initiate at surface irregularities such as dislocations, grain boundaries, or locations of non-
metallic inclusions.(3) For example, sulfide inclusions in austenitic and ferritic stainless steels
have been shown by many investigators to be favored initiation sites.(4-8) Pit shape and density
depend on the crystallographic orientation of the surface exposed.(3)
Breakdown of the passive film can occur for several possible reasons and three types of models
have been proposed to describe the pitting initiation process(4):
1. Adsorption and adsorption-induced models in which the adsorption of aggressive anions like
chloride is central
2. Ion migration and penetration models
3. Mechanical film breakdown models
The point defect model (PDM)(3, 9) proposed by Macdonald, et al.(10, 11) provides an explanation
for the stages of pit nucleation as shown schematically in Figure 2-2. This figure shows the
steady state growth condition where a passive film grows on the metal surface. In the steady
state condition, the rates of film formation at the metal/film interface and the rate of film
dissolution at the film/solution interface are in balance (Figure 2-2a).(9) Transport of metal ions
through the oxide film occurs. However, if the film growing at the film/metal interface is
disrupted (Figures 2-2 b and c) subsequent straining or dissolving of the partial film can lead to
rupture (Figure 2-2 d). One means by which the film can be broken down according to the PDM,
is by the condensing of cation vacancies arriving at the metal/film interface, that is, by
generation of more cation vacancies at the film/solution interface than can be absorbed at the
metal film/interface. When the voids reach a critical size, the passive film collapses leading to
pit growth.
2-4
The steps shown in Figure 2-2 a-d can be considered the nucleation stage of pitting with either
subsequent re-passivation or pit growth by dissolution of the metal (Figure 2-2 e).
Figure 2-2
Schematic Outlining Various Stages of Pit Nucleation According to the Point Defect Model
Source: Reference 9
In cases where the pitted surface does not re-passivate, corrosion within the pit (pit growth) can
be rapid and essentially independent of the external environment.
Pit growth is considered to be an autocatalytic process: the environment within the pit supports
the continued activity of the corrodent. In HRSG tubing, for example, deposition of corrosion
products and anions in the water (chloride, sulfate, etc.) support initiation of pitting. High levels
of dissolved oxygen, as exist during unprotected unit shutdown, layup and startup periods, serve
to make metal surfaces more susceptible to pitting corrosion. Pitting is most prominent under
stagnant conditions. The fact that the fluid is static allows the initiation of pitting to occur
unimpeded. Stagnant conditions allow for the concentrations needed to accelerate the attack.
Once initiation has begun (such as during an unprotected shutdown of the unit) then continued
growth of the pit will occur during each unprotected shutdown. These pits can also initiate
cracks during operation; this is of particular concern in steam turbines especially if the surfaces
were contaminated during service. However, pitting can occur even during normal steam turbine
operation as a consequence of impurity concentration effects within the liquid films present on
surfaces within the phase transition zone (PTZ).
The interface of the remaining fluid with the environment is a particularly corrosive area. Thus
the air water interface in components maintained wet without nitrogen blankets or, in drained
components, any remaining accumulations of water such as in tubing or piping u-bends or on
horizontal surfaces are areas which are extremely prone to pit initiation and growth.
2-5
Pit growth is often influenced by gravity, which accounts for the susceptibility of horizontal
surfaces to attack. The formation of a dense, concentrated solution and its retention favors the
propagation of the pit, a process that is facilitated if the pit is oriented downward, to the pull of
gravity.
2.2.2 Protection of Copper Alloys
As stated previously, use of copper alloys in the feedwater part of combined cycle units is not
common. Nevertheless, some combined cycle units may include some copper in the feedwater
system though the surface area of copper in combined cycles is likely to be very low relative to
that present in conventional cycles. Also, combined cycle units with all ferrous feedwater
metallurgy may utilize copper alloys in the condenser.
Research conducted under EPRI’s Program Copper demonstrated that satisfactory protection of
copper alloys in the feedwater of conventional cycles under typical operating conditions requires
that a reducing environment (with a reducing oxidation-reduction potential) be established and
maintained).(12-15) Failure to continue to provide a reducing environment during shutdown, layup
and startup is very disruptive to the protective oxide layer of cuprous oxide, Cu2O and would
result in significant copper transport activity. However, it should be kept in mind that the
reducing environment favorable to copper is known to exacerbate flow-accelerated corrosion
(FAC) damage in steels; a 2004 survey determined that FAC was the most prevalent HRSG tube
failure (HTF) damage mechanism.
Copper alloy condenser tubes, on the other hand, exist in an oxidizing environment at all times
(even when the feedwater part of the plant operates in a reducing environment) and are subject to
low operating temperatures as compared to feedwater heaters. Thus it is possible and
advantageous to utilize oxidizing chemistries in cycles with all ferrous feedwater systems of
combined cycles even if a copper alloy is selected for the condenser tubes.
2.3 Guiding Principles Governing Protection of Cycle Components During

Shutdown, Layup and Startup
Operating experience, as reflected in the survey results of fossil plant chemistry personnel
presented in Section 1(16), makes it clear that efforts to protect equipment during outages is often
unsatisfactory. It is also apparent that some of the serious problems chemistry personnel face
involve the shutdown/layup/startup period. Further, it is clear that many steam generator tube
failure mechanisms, both chemical and non-chemical, are influenced by the operating practices
followed at this time. The research activities of EPRI continue to yield findings supporting these
observations and confirming that it is very important to maintain a protective chemical
environment during fossil unit shutdowns.
In view of the foregoing, it becomes apparent that operators of fossil units need to place greater
emphasis on equipment protection during shutdowns. The objective of such action is to eliminate
pitting and general surface corrosion as this will maintain the stability of protective metal oxides
formed during normal operation. Successful implementation of equipment protection serves the
2-6
broader purpose of minimizing damage by other mechanisms which are active when the unit is in
service.
Guiding Principles for protection of fossil plant equipment, developed by EPRI and based on
worldwide experience including EPRI’s application of an integrated HTF reduction program and
cycle chemistry program, need to be kept in mind when addressing chemistry control during unit
shutdown. These guiding principles are applicable to both combined cycle units and
conventional fossil units.
In order to avoid damage to water and steam touched surfaces of cycle components during
shutdown and layup periods a seamless transition from service through the shutdown, during the
time out of service (protected layup) and the subsequent startup to return the unit to service is
needed. The science of corrosion during idle periods is well understood and clearly points to the
following Guiding Principles which, if considered in unit operating practices and procedures will
prevent damage:
1. Keep the Potential of Water in the Cycle the Same During All Operating Conditions.
This requires:
• When using oxidizing all-volatile treatment (AVT(O)) or oxygenated treatment (OT) as the
feedwater treatment, not adding reducing agents during shutdown, layup or at startup, and
actively keeping air out of the cycle.
• When using reducing all-volatile (AVT(R)) feedwater treatment, keeping the potential
reducing by keeping reducing agent in the water during shutdown and actively keeping air
out of the cycle.
• With all feedwater and evaporator water treatments, operate as needed to comply with
Guiding Principle 2.
It should be noted that, for combined cycle units, the preferred feedwater treatment is AVT(O).
Treatment selection criteria for feedwater and evaporator water are provided in EPRI’s cycle
chemistry guidelines. (18)
2. Keep Water from Becoming Oxygenated by the Surrounding Environment.
This requires:
• Avoid air ingress during shutdown by maintaining condenser vacuum as long as possible.
• Keep oxygen out of water during layup by nitrogen blanketing. The nitrogen system should
have multiple entry points to ensure all pressure circuits are covered.
• Avoid stagnant, oxygenated water conditions, which can lead to pitting corrosion; a small
circulation of the fluid will prevent the stagnant conditions.
• Use high purity water of low oxygen content to fill equipment prior to startup and as cycle
makeup during the startup. This will entail using a nitrogen sparging system in the storage
2-7
tank, use of a gas transfer membrane or elevating the temperature of the water in the storage
tank.
• Use auxiliary steam at startup to prevent air ingress at deaerators during startup.
3. Keep Water and Moisture out of Steam Touched Components and any Water Touched
Surfaces to be Maintained Dry during the Shutdown Period.
This requires:
• Use of warm dehumidified air to protect steam turbines (particularly the LP turbine) and
reheaters.
• Rapid draining of normally water touched components while they are still hot; this will result
in flashing of residual water prior to dry layup or activities such as equipment inspection or
maintenance.
The operator should regard each unit shutdown as a unique event. A means of equipment layup
effective in protecting all water and steam touched surfaces must be implemented by the
operator; layup practices must consider and be consistent with unit design and operation, but also
be in line with the Guiding Principles.
Protection of cycle steam and water touched surfaces is important during both planned and
unplanned shutdowns. The Guiding Principles must become a key part of the plant operation
procedures. For example, equipment inspection, repair and maintenance requirements, when
applicable, will vary and must be accounted for when implementing equipment protection
procedures, but in all cases the Guiding Principles are of paramount importance. Shutdowns
involving such activities require special attention; further action may be needed before
transitioning the unit from the shutdown to the layup condition. Under all circumstances,
transition to the layup condition must be seamless, particularly if wet layup is to be used.
Similarly, when evaluating new shutdown and layup procedures or returning to service from an
unusual outage condition the Guiding Principles must be thought of first. Such an example might
be after a chemical cleaning. In all cases it is necessary to monitor cycle chemistry during
startups and initial unit operations as needed to assess the adequacy of the equipment protection
measures during the shutdown.
The optimal protection strategy for a particular unit will naturally depend on site-specific factors.
These include unit design and operational requirements. The strategy will also need to consider
the requirements of the outage and its expected duration. Regardless of the specific requirements,
the Guiding Principles outline the general requirements applicable in virtually all circumstances
that operating personnel should adopt when determining the best strategy to employ in individual
combined cycle units.
2-8
2.4 Unit Outages and Shutdowns
Successful protection strategies to be followed should always consider the guiding principles for
equipment protection. They should also consider the purpose of the outage and the expected
duration of the shutdown period.
Optimal equipment protection during outages will typically depend on the nature of the
shutdown and the purpose of the ensuing outage.
Most shutdowns (including shutdowns for economy) are of an elective nature; they typically
occur with some advance notice and usually offer at least some flexibility in timing and should
thus be controllable by the operators of the unit. The shutdown should be initiated with
equipment protection in mind, even if the duration of the outage is uncertain. Unless there is a
specific need to work on the equipment and there is assurance that the shutdown duration will
allow it, opening of equipment is generally not practiced during economy outages.
Unplanned shutdowns that are forced due to reasons such as mechanical problems in the plant,
severe water chemistry excursions, loss of connection to the grid or other causes occur with little
or no advance notice and may restrict the ability of the operator to control the shutdown.
Circumstances will determine the nature of the ensuing outage, and it is frequently necessary to
open equipment for inspection and repairs. However it is still important to plan for protection of
all water and steam touched surfaces comprising the cycle.
Outages are required for various reasons. Depending on cost of power from competing sources,
economy is often a common reason for outages in combined cycle units. Outages may be needed
for short term action such as repairs of mechanical equipment or initial resolution of component
damage such as evaporator or water cooled condenser tube leaks. Longer outages are typically
needed in instances where more extensive repairs are required, including off-site repairs, and for
scheduled major maintenance and inspection activities.
The guidelines for layup presented in Section 3 look at short term, intermediate term and
longterm layup, as well as the protection requirements of extended outages. These guidelines
consider both the duration of the outage and the purpose. Determination of the most suitable
approach to equipment protection must be made at the plant level, in consideration of the guiding
principles for equipment protection, the choices for layup outlined in Section 3 and specific
needs of individual units.
2.4.1 Short Term Outage
Short term outages may be defined as outages during which oxygen can be excluded from the
system and temperatures can be maintained high enough to avoid condensation on surfaces and
facilitate flashing of liquid on surfaces if the cycle should need to be drained. In many combined
cycle units it is not possible to maintain condenser vacuum for more than about 24 hours after
shutdown; the most common application of short term protection applied to overnight
shutdowns. The duration can be extended somewhat if the condenser steam space and steam
turbine can be protected by introduction of dehumidified air (preferred) or nitrogen. Use of
2-9
nitrogen to blanket other parts of the cycle as temperatures fall and pressures decrease is also
desirable. Steam blanketing of equipment, where possible and affordable, also helps to both
exclude oxygen and maintain temperature during the outage.
2.4.2 Intermediate and Longterm Outages
Outage protection needs change when it is no longer possible to maintain satisfactory short term
protection; operators of combined cycle units need to recognize the capability and limitations of
individual systems and define the boundary between short term and longer term outages
accordingly.
Intermediate term protection becomes necessary when short term protection is no longer
practical or possible. A typical duration would include weekend shutdowns and outages of up to
about five days.
Longterm protection methods are typically effective for several days or even a few weeks as
needed; this period is dependent on several factors and proper monitoring is needed to assure that
the protection remains effective. Continuation of intermediate outage protection measures may
be effective. With longer anticipated outage durations, more reliable protection may be expected
through use of dry layup procedures.
2.4.3 Extended Outages
Organizations operating in markets with low power costs, and high generating capacity may elect
to consider extended protection covering several weeks when operation of their combined cycle
unit assets is not economically competitive. Protection may well be possible through
continuation of longterm or even intermediate protection measures. In all cases protection
measures applied should effectively address all of the guiding principles of Section 2.3.
The strategies presented in Section 3 of these guidelines address only the water and steam
touched surfaces of the steam-water cycle in detail for the above outage conditions. Some
general guidance is provided with respect to protection of other areas of combined cycle units.
2.4.4 Outages Requiring Plant Mothballing Protection
In some cases protection of plant equipment could be needed for many months or possibly years
and consider equipment and systems beyond the boundaries of the steam-water cycle. These
guidelines are not intended to cover situations where mothballing of units will be required as a
long range strategy.
2-10
2.5 Unit Design Factors Influencing Combined Cycle Unit Shutdown, Layup
and Startup
Many aspects of the unit design will influence shutdown, layup and startup. Ensuing discussions
review the more common factors, emphasizing their influence on corrosion, corrosion product
transport, and other cycle chemistry effects.
2.5.1 HRSG Tubing and Gas Path Arrangement
While designs that employ horizontal gas paths and vertical tubing are most common (Figure
2-3), HRSGs with vertical gas paths and horizontal tubing (Figure 2-4) are also in use. With
either arrangement, all heat input may be derived entirely from combustion turbine (CT) off
gases, or from a combination of CT off gases and firing of supplemental fuels in duct burners.
Circulation pumps are not normally provided on horizontal gas path designs but may be included
in vertical gas path designs. Circulation capability can be advantageous for wet layup protection
of the HRSG as it will help in compliance with the second guiding principle..
2.5.2 Evaporator Circuit Design
While most evaporator circuits are of the drum type, there are a few HRSGs with once-through
circuits; most of these units are in North America. Some designs include a drum type low
pressure (LP) circuit, while in others this circuit is also of once-through design.
In selection of cycle chemistry, each evaporator circuit must be considered as a separate system,
while also considering the needs of rest of the HRSG. Combined cycle units can be placed in
service very rapidly and thus it is crucial during startup to monitor drum levels and carryover
carefully. Otherwise uncontrolled drum level increases could result in introduction of solids
based chemicals (trisodium phosphate and caustic) to the saturated steam. Depending on
sensitivity of the unit in question, it may be necessary to limit evaporator circuit dosing startup.
2.5.3 System Drains and Vents
Drains are sometimes undersized or arranged in a way that inhibits complete draining of steam-
touched circuits at startup. This can result in blocked tubes which contribute to thermal stress and
fatigue type damage and failures as is discussed extensively in other EPRI publications.(2, 17)
Drain connections on water touched circuits can serve as a bottleneck and may inhibit the ability
to drain these circuits quickly and completely while the metal is still hot. Based on experience in
conventional boilers, it seems likely that horizontally tubed circuits will likely be slower to drain
and more difficult to drain completely than vertically tubed circuits. Draining and venting
characteristics can have direct bearing on compliance with each of the three guiding principles.
2-11
Figure 2-3
Natural Circulation, Vertical Tubed, Multi-pressure HRSG(2)
2-12
Figure 2-4
Horizontal Tube Typical Configuration for Drum-type HRSG(2)
2-13
2.5.4 Materials of Construction
Cycle materials will have direct bearing on the method of layup selected; further discussion is
provided in Section 2.2 and in Section 3.1.2 of these guidelines.
2.5.5 Cycle Chemistry
The guidelines of Sections 3, 4 and 5 reflect the choice of operating feedwater and evaporator
circuit chemistries. As discussed earlier, the choice of the feedwater treatment (almost always
AVT(O)) is dependent on cycle materials, which has direct implications on wet layup treatments
since the chemistry environment (potential) should be constant during all operating conditions.
As clearly indicated in the first guiding principle, the potential should not be allowed to drift
between oxidizing and reducing conditions, meaning that use of reducing agents to protect
systems operated with AVT(O) is not allowed.
Evaporator treatments can have implications on combined cycle unit startup. Solids based
treatments such as phosphate continuum (PC) and caustic treatment (CT) offer possible benefits
in avoidance of corrosion fatigue damage at startup. Their use at startup is also beneficial in the
event undetected cycle contamination is present. However, these chemistries cannot be used in
low pressure (LP) evaporator circuits that provide attemperation water to superheater and
reheater circuits or when the LP evaporator supplies water to other evaporator circuits. Also,
their use during startup could be problematic in drum circuits that are prone to drum swelling,
sudden level increases and mechanical carryover during startups.
In older conventional cycles with drum boilers, use of solids based treatments was often
preferred during unit commissioning, even if the intention is to use volatile chemistry during
commercial service since cycle integrity is not known. However, in view of possible steam purity
concerns, the opposite approach has actually been taken in some combined cycle systems.
In new combined cycle units that will be operated on solids based evaporator treatments in any
circuit, it is sometimes considered prudent to conduct the initial operations during the
commissioning of the HRSG with volatile chemistry until the sensitivity to carryover as a result
of drum level increase at startup is known. Carryover testing of each circuit is regarded as
mandatory during the commissioning period. Further, carryover is now an EPRI core monitoring
parameter for normal operation.
In at least some cases, it will likely be found to be better to continue to start the unit up on
volatile chemistry and introduce the solids based treatment at some minimum load that has been
demonstrated to support stable control of drum level in the evaporator circuits. Operating
procedures for unit shutdown should be made as needed to accommodate this approach. In
others, it may be suitable to maintain the operating chemistry in the boiler during shutdowns
where the HRSG is to be protected in a wet condition.
2-14
2.5.6 Turbine Bypass Systems
Turbine bypass systems are often installed on many newer combined cycle systems with reheater
circuits as a means to minimize thermal transients. Another benefit is to establish suitable steam
purity prior to closing the bypass. Use of bypass systems also minimizes the risk of steam turbine
damage by oxides and foreign objects; however, it should be recognized that any solids entrained
in the steam when the bypass is open will enter the condenser.
2.5.7 Condensate Polishers and Filters
Condensate polishing is not available on most combined cycle units; the main exceptions are
some units with either once-through evaporators or air cooled condensers. Use of these polishers,
where provided, can help clean up the cycle during unit startup. However, conducting unit
shutdown, layup activities in accordance with the guiding principles of Section 2.3 will serve to
reduce the need for cycle cleanup during startup.
Polishers allow for both dissolved solids capture via ion exchange and filtration of metal oxides.
Filtration capability is particularly beneficial in units with air cooled condensers as there is often
high iron transport, especially during early service operations and during unit startups. Polishers
and filters are worth considering as part of the design of any combined unit but offers greatest
value in units that are subject to peaking service operation.
Typically, units with these systems will include recirculation lines to maximize cleanup early in
the startup. Units with polishers and steam bypass systems are also well suited to cleanup of the
condensate as part of the startup process.
2.5.8 Condenser Air Removal and Feedwater Deaeration Capabilities
The latest EPRI cycle chemistry guidelines recognize the importance of controlling condenser air
in-leakage and reducing dissolved oxygen at the condensate pump discharge to <10 ppb.(18)
Attainment of this criterion requires that air in-leakage be well controlled, particularly at
locations beneath the water level in water cooled condensers. The air removal system must be
sized to quickly establish vacuum at startup and also capable of maintaining the condensate
system under vacuum until other equipment protection measures (dehumidified air, nitrogen
blanketing or auxiliary steam blanketing) can be implemented. Such capabilities are integral to
compliance with the second guiding principle. Further discussion of this important subject is
included in Appendix C.
2.6 Application of These Guidelines to Individual Combined Cycle Units
As indicated in the previous discussion, there is a multiplicity of factors that will influence the
chemistry during shutdown, layup and startup. Many of these factors can influence the
effectiveness and even the applicability of the choices that must be made for shutdown and layup
of combined cycle units, as outlined in Sections 3 and 4. It is thus quite clear that no guidelines
or road map could adequately address all possible plant designs, operating requirements, outage
2-15
conditions, etc. Determination of the optimum approach to shutdown, layup, and startup must be
consistent with the guiding principles of Section 2.3 for equipment protection. This assessment
and customization approach will result in detailed procedures and, where needed, engineering
solutions that best meet the needs of the individual unit. Practices and procedures which deviate
from the guiding principles (or simply taking no action at all to protect the cycle) will inevitably
lead to the various problems presented earlier with unavoidable losses in unit availability and
performance.
2.7 References
1. K. J. Shields and A. F. Aschoff, “Influence of Steam Generator Shutdown, Layup and Startup
Chemistry Control Practices on Steam Generator Tube Failures”. Proceedings: Boiler Tube
and HRSG Tube Failure and Inspection International Conference: November 2-4, 2004, San
Diego, California, EPRI, Palo Alto, CA: 2004. (Publication pending.)
2. Heat Recovery Steam Generator Tube Failure Manual. EPRI, Palo Alto, CA: 2002. EPRI
1004503.
3. H. Bohni, “Pitting and Crevice Corrosion”, in M.O. Speidel and A. Atrens, eds., Corrosion in
Power Generating Equipment. Plenum Press. New York, 1984, pp. 29-48.
4. P.E. Manning, et al., Corrosion, 38, 1980, p. 313.
5. J. Degerbeck, Werst. Und Korrosion, 29, 1978, p. 179.
6. M. Henthrone, Corrosion, 26, 1970, p. 511.
7. Z. Szdarska-Smialowska, et al., Br. Corr. J., 5, 197, p. 159.
8. B.R.T. Anderson and B. Solly, Scand J. of Metallurgy, 4, 1975, p. 85.
9. D.D. Macdonald, “The Point Defect Model for the Passive State”, Journal of the
Electrochemical Society, Volume 139, No. 12, February, 1992, pp. 3434-3449.
10. C.Y. Chao, L.F. Lin, and D.D. Macdonald, J. Electrochem. Soc., 128, 1981, p. 1187.
11. L.F. Lin, C.Y. Chao, and D.D. Macdonald, J. Electrochem. Soc., 128, 1981, p. 1194.
12. State-of-Knowledge of Copper in Fossil Plant Cycles. EPRI, Palo Alto, CA: 1997. TR-
108460.
13. Guidelines for Copper in Fossil Plants. EPRI, Palo Alto, CA. EPRI 100457. November
2000.
14. Copper Alloy Corrosion in High Purity Feedwater: Admiralty Brass, Aluminum Brass, and
90/10 Copper/ Nickel at 95°C (203°F). EPRI, Palo Alto, CA: 2003. 1007391.
15. Influence of Water Chemistry on Copper Alloy Corrosion in High Purity Feedwater. EPRI,
Palo Alto, CA: 2003. 1007612.
2-16
16. Survey Results, Proceedings: Seventh International Conference on Cycle Chemistry in Fossil
17. Delivering High Reliability HRSGs. EPRI, Palo Alto, CA: 2003. 1004240.
18. Cycle Chemistry Guidelines for Combined Cycle Heat Recovery Steam Generators
(HRSGs), EPRI, Palo Alto, CA: 2006. 1010438.
2-17
3
SHUTDOWN AND LAYUP TECHNIQUES FOR WATER
AND STEAM TOUCHED SURFACES OF COMBINED
CYCLE PLANT COMPONENTS
3.1 Introduction to Shutdown and Layup of Combined Cycles
A review of the failure mechanisms in combined cycle plants(1-3) indicates that stresses and
chemistry changes imposed by cyclic operation account for most of the damage to HRSG
pressure parts. Unit startup and shutdown impose significantly more potential for damage than
steady-state operation. Allowance for these conditions must be considered early in the design
phase of the unit.
Two actions recommended during design are(1):

• Develop detailed integrated unit startup, shutdown and operating procedures early in the
design process, to be refined and confirmed during commissioning and operation.
• Design appropriate hardware and controls required to ensure proper ability to achieve the
developed operating procedures.
In providing these actions, it is implicit that the design assessment should also assess the
protection requirements that are likely to exist during commercial operation of the plant and
consider systems and equipment that would be needed for effective layup.
There are only two major equipment design options available for conventional units, drum and
once through, although there are many variables relative to pressures, temperatures and balance
of plant equipment. The situation is much more complex in combined cycle design
configurations. Combined cycle units include, at present, one to three separate pressure
evaporator circuit designs and may include drum circuits, once-through circuits and
combinations of drum/once-through circuits. Even though combined cycles are of increasingly
complex design, the principles of layup, startup, and shutdown are similar to those used in
conventional units and the guiding principles of Section 2.3 must be adapted and applied.
However, some aspects of layup, startup and shutdown will need to be modified from the
guidelines given herein to account for unique differences in equipment, design and operation vs.
conventional units. For example, combined cycles may or may not include stand-alone
deaerators; reheaters; and, a feedwater heater(s), among other differences; however, protection of
steam and water touched surfaces based on the Section 2 guiding principles applies to all
pressure values and cycle configurations.
3-1
Shutdown and Layup Techniques for Water and Steam Touched Surfaces of Combined Cycle Plant Components
A summation of important differences in actual HRSG configurations has been tabulated in a

recent EPRI publication.(2) These include, but are by no means limited to the following:
• HRSG design concepts and details
• Single pressure, dual pressure, and multi-pressure designs
• Vertical and horizontal tube/flow designs
• Inclusion of reheaters is now common, but was not included in the design of most early
operating units
• Natural circulation, assisted circulation, or forced circulation
• Drum or once-through evaporator circuits
• Balance of plant (BOP) design differences
• Supplemental (duct) firing
• Multiple fuel options
• Exhaust bypass and/or stack closure dampers may or may not be present
• Feedwater heaters/preheaters may or may not be present
• Selective catalytic reduction (SCR) for NOX control and oxidation catalyst for CO abatement
may or may not be present
• Water from the LP circuit may or may not be fed to IP and HP circuits
• Water from the IP circuit may or may not be fed to the HP circuit
• Cascade blowdown may be practiced on multiple pressure drum HRSGs
• Attemperation water may be taken from various sources
• Deaeration may be performed only in the condenser or using a deaerator in the feedwater
system or LP circuit,
• Condenser may be water cooled or air cooled
• Condensate polishers may or may not be present
Therefore, because of the complexities of design inherent in today’s combined cycles, it is

impossible to address all procedural aspects of layup, startup and shutdown, which could be
encountered in modern combined cycle design. The discussion which follows will concentrate
on the general principles of this topic, assuming the individual operators will have enough
information from the ensuing discussion to adapt the processes described herein to fit the
equipment being operated.
3.1.1 General Layup Considerations
Flow accelerated corrosion (FAC) is perhaps the most important HRSG tube failure mechanism
in combined cycle plants. A 2004 survey by EPRI determined it to be the ranked first by the
3-2
participants.(4) FAC is strongly influenced by the feedwater chemical composition, which

benefits significantly through operation in the oxidizing mode, all-volatile treatment (AVT(O))
or oxygenated treatment (OT) as described in the recent EPRI publication “Cycle Chemistry
Guidelines for Combined Cycle/Heat Recovery Steam Generators”.(5) Operating in the AVT(O)
or OT mode will reduce iron concentrations in the cycle and minimize the occurrence of single-
phase FAC.
The alternate feedwater system is AVT(R) which requires the use of a reducing agent
(hydrazine) in addition to a pH control chemical (ammonia). This system, which is mandatory
for HRSG cycles with mixed metallurgy, is not required, nor is it desired for the all-ferrous
feedwater systems (exclusive of the condenser tube materials) commonly used in combined
cycles with HRSGs.
Since the vast majority of HRSG installations today utilize all-ferrous feedwater systems, and
because of the advantages of operations in the oxidizing mode, it is the EPRI philosophy to use
either AVT(O) or OT, rather than AVT (R) for HRSG feedwater systems with all-ferrous
metallurgy (again excluding the condenser). Therefore, this document is focused primarily on
all-ferrous units operated in the oxidizing regime.
The two types of layup applicable to all types of units, conventional and combined cycle, are
classified as “wet” or “dry”. For short term protection, it is generally permissible to simply keep
the same water chemistry as during normal operation while taking measures to exclude oxygen
such as keeping equipment hot and maintaining condenser vacuum. Wet layup for longer
shutdown periods requires the filling of most of the system with an alkaline solution and
preventing air ingress by pressurizing with nitrogen. The use of wet layup solutions in AVT(O)
or OT units should generally be restricted to short term protection, since the guiding principles
clearly indicate the use of hydrazine is not allowed wet layup solutions for units operated under
oxidizing conditions. Extended wet layup without a reducing agent in these types of units will
lead to pitting attack unless the equipment is reliably nitrogen capped and there is a means
provided to periodically circulate the layup solution. In view of these concerns, dry layup
methods are clearly preferred for all but short term protection of OT and AVT(O) units. (Wet
layup of HRSG cycles with mixed metallurgy feedwater systems operating on AVT(R) involves
filling applicable circuits with a solution containing ammonia and hydrazine and applying a
nitrogen cap according to the duration of the shutdown.)
Dry layup requires draining the units while hot, and removal of all water followed by use of
dehumidified air or pressurization with a moisture-free inert gas (nitrogen) to maintain a low
moisture environment.
3.1.2 Shutdown, Layup and Startup of HRSGs with Multiple Evaporator Circuits
The HRSG will often include two or three evaporator circuits, operated at different pressures.
While in some cases it may be possible to utilize a common evaporator treatment in each circuit,
there are many instances where the chemistry selected should be different for the individual
pressure stages. For example, in HRSGs with three drum evaporator circuits, a solid alkali is
often added to the low pressure (LP) and possibly intermediate pressure (IP) circuits for FAC
3-3
protection where not prohibited by use of water from the LP circuit for steam attemperation.
Users of these guidelines are referred to the revised HRSG Cycle Chemistry Guidelines for
further details on chemistry selection and optimization.(5) Where different chemistries are in use,
the shutdown, layup and startup practices to be followed should be selected accordingly as
required by the guiding principles for equipment protection.
Ideally, the evaporator chemical conditions during shutdown and short term layup would
normally be the same as during operation. However, care would be needed to ensure that during
the ensuing startup, the chemical conditions (e.g. PC or CT) in one pressure stage (e.g. LP) do
not adversely affect the chemical conditions in other pressure stages, for example through the use
of water from one evaporator circuit as feedwater to another as is required in some designs. Of
more widespread concern is the possibility of carryover in drum evaporator circuits during
startups when using phosphate continuum or caustic treatment. These concerns are greatest
during cold starts, when heating of the cold water will sometimes lead to swings in level in the
drum circuits, possibly resulting in introduction of any solids in the evaporator water to the steam
via mechanical carryover. Startup procedures for HRSG circuits containing solids based
treatment chemicals must be alert to this possibility.
For longer shutdowns it will be necessary to change the chemistry, or preferably drain the
circuits for dry layup protection. The shutdown discussions of Section 4 address shutdown for
each of the available evaporator chemistries. The startup requirements for each evaporator circuit
will still depend on the operating treatment applied; guidance is included in Section 5.
Carryover characteristics for each drum evaporator circuit should be carefully evaluated during
unit commissioning and early commercial service under all startup and operational conditions.
This is particularly important because combined cycle plants are placed in service rapidly and
frequently include HRSG drum evaporator circuits with relatively small drums and simple steam
separator devices, as compared to those present in conventional cycles with radiant drum boilers.
To avoid the risk of steam path contamination by solids-based treatments during commissioning,
some manufacturers have elected to place all circuits of the HRSG in service on AVT until
pressures and drum levels have stabilized, at which time PC or CT treatment would be
introduced, where allowable and desired. This approach would appear to be especially useful
during cold startups of commercial units where level control problems have been experienced.
Following this option could expose the HRSG to corrosion if the feedwater is contaminated so it
is essential to carefully monitor the chemistry during the startup.
In summary, there are several factors that must be considered with respect to evaporator
chemistry during shutdown, layup and startup of HRSGs with multiple evaporator circuits. When
the HRSG features more than one evaporator stage, it is first necessary to consider the operating
chemistry and treatment needs of each circuit through the selection and optimization process.
Shutdown, layup and startup procedures must consider the treatments in use and the guiding
principles for equipment protection. It is necessary to understand the startup characteristics of the
unit and anticipate the startup conditions that will follow the shutdown. For effective chemistry
management of drum evaporator circuits employing PC or CT, it is clearly important that the
operator have a good understanding of the drum level and carryover tendencies. The shutdown
3-4
should be planned based on this knowledge, as well as the purpose and the expected duration of
the outage.
3.1.3 Feedwater Systems Containing Copper
As mentioned in Section 2, the metallurgy of the feedwater system must be carefully considered
when establishing chemistry parameters for startup, shutdown, and layup. As most combined
units are designed with all ferrous feedwater systems, subsequent discussions are directed to
protection measures for these cycles.
For the few combined cycle units with feedwater systems containing copper alloys, it is most
important to maintain a reducing atmosphere (ORP < 0mV) at all times through operation with
AVT(R). During operation this is generally accomplished by the use of suitable concentrations
of hydrazine to establish reducing conditions and with addition of ammonia to regulate pH in the
range of 9.0-9.3. The reducing environment must also be maintained during shutdown and layup
periods. Oxygen ingress must be avoided, as this will increase the corrosion rate of copper
alloys by changing the predominant surface oxide to cupric oxide.
The cycling of units, accompanied by periods of layup, materially increases the risk of copper
alloy attack, because of the opportunities for oxygen ingress with associated increases of ORP
into the oxidizing range. Therefore, chemistry control under these conditions requires much
more attention than for baseloaded units.
The reader is referred to the HRSG cycle chemistry guidelines(5) for further discussion of mixed-
metallurgy feedwater systems for combined cycle units operating with AVT(R) feedwater
chemistry.
3.2 Roadmap for Selection of Layup Techniques for Use in Combined

Cycle Units
A generic road map indicating layup procedures suitable following shutdown of combined cycle
units is shown in Figure 3-1. Because of variations in design, some generating units may require
deviations from this road map, or may require customization to adapt to a particular plant design
as previously discussed. Figure 3-1 is divided into eight steps, which are further described as
follows.
3-5
Figure 3-1
Road Map for Shutdown and Layup Guidelines Common to Most Combined Cycle Units
3-6
Step 1 – Short Term Shutdown
Short-term layup presumes that the unit will be required to operate within a relatively short time
frame. Protection is based on the guiding principles that the potential of the water should be kept
the same during all operating conditions. During short term shutdowns it is expected that the
pressure will not decay to atmospheric which is consistent with the second guiding principle
stating that the water should not be allowed to become oxygenated by the surrounding
environment. Thus no major changes are required from normal operating conditions, with the
exception being that the unit must be protected from air ingress. The condenser vacuum and
turbine seals are maintained; and, the deaerator and heater shells (if provided) and HRSG are
capped with nitrogen or steam. The feedwater chemistry is maintained according to the
requirements of the AVT(O) or (OT) treatment employed.
If short term protection cannot be maintained before the units will be returned to service, it
should receive protection suitable for a longer shutdown period.
Step 2 – Intermediate, Longterm and Extended Shutdown
Intermediate, longterm and extended shutdowns require additional steps to be taken to prevent
corrosion during intermediate shutdown periods, such as for maintenance and indeterminate
cycling or peaking requirements; and during longterm or extended shutdowns. Certain actions,
described here, are common preparation requirements regardless of shutdown duration, and
whether the unit is to be laid up dry (Step 3 or 4) or wet (Steps 5-7).
As the shutdown period increases there is a danger of off-load corrosion (pitting) if the water in
any vessels or tubing becomes oxygenated. Thus a wet layup approach needs to carefully
consider the requirement of the second guiding principle stating that the water must not become
oxygenated and further that stagnant conditions should be avoided.
During shutdown, protection of steamside surfaces of the turbine, condenser and any reheater
circuits are generally considered together because, unless special facilities are provided (most
likely for an extended shutdown or mothballing) there is no practical way to isolate them. For
Step 2, reheater circuits should be evacuated with the condenser still under vacuum. Nitrogen
should be introduced for purging of the reheater and draining of the condenser. It is preferable to
conduct the evacuation procedures at temperatures above ambient. For this reason, vacuum
drying should be applied immediately after the unit is drained hot. An additional heat supply is
advantageous.(6) Hot draining with subsequent vacuum drying should be also used if the dry
layup will be applied after repairs to some pressure parts of the HRSG. If the unit is connected to
any external steam sources, such as auxiliary steam systems, all isolation valves must be tight to
prevent moisture entry into the unit during shutdowns. Again, these actions must be taken to
avoid oxygenation of the water in accordance with the second guiding principle.
With special facilities incorporated, the superheater and reheater can be isolated from the turbine
and may be stored wet (see Step 7 of roadmap). The turbine, however, can only be laid up dry.
Utilization of warm, dehumidified air (Step 3) in accordance with the third guiding principle
stating that water and moisture must be excluded from surfaces to be maintained dry is
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considered the best approach to protection of these components. It is also considered a very
useful approach for more widespread protection of the HRSG and other steam-water cycle
components during shutdown periods. Protection of the turbine by a continuous nitrogen purge
(Step 4) is another available option.
Step 3 – Dry Air Layup and Step 4 - Dry Layup with Nitrogen
The dry layup procedures require that all components of the system be drained and dried in
accordance with the third guiding principle from Section 2.3 which requires elimination of water
and moisture. Draining of water in steam-touched systems occurs at a residual pressure of up to
300 psi (about 2 MPa) depending on the configuration and the construction of the unit. Any
remaining water in the entire system may be evaporated under vacuum using the unit evacuating
equipment (e.g., evacuation of connected systems: feedwater line, heater(s) (if furnished),
HRSG, main steam lines, HP bypass, cold reheat line, reheater, hot reheat line, IP bypass,
condenser). Experience indicates that the circuits of many HRSGs are not designed for effective
draining. Personnel responsible for equipment protection should be aware of this possibility and
consider means to shorten the time and improve the thoroughness of drain procedures. If needed,
these procedures can also be used during extended shutdowns.
For Step 3, Dried Air Layup, protection with warm, dry air layup requires that all components of
the system be drained and dried quickly, in accordance with the third guiding principle, and
maintaining dry air flow through the system. The intent is to reduce the relative humidity of the
air in the equipment being protected to levels (<40 % and typically 30-35%) at which corrosion
will not develop. Use of warm, dry air provides excellent protection during extended outages and
is widely and successfully used for plant mothballing. The equipment required for dry layup is
described later in this section, together with the advantages and disadvantages relative to wet
layup protection.
Entry of protected equipment for inspection and maintenance is possible when employing dry
layup with warm, dehumidified air. It is of course necessary to follow all relevant plant safety
precautions that apply. To minimize the risk of moisture formation, points of access should be
opened for the minimum time and to the minimum extent practical.
When selecting Step 4, Dry Layup with Nitrogen, nitrogen gas is used for blanketing equipment
while and after it is drained; surfaces of protected surfaces do not need to be completely dry.
Protection is obtained through conformance to the second and third guiding principles. After
draining, nitrogen is applied to establish and maintain a positive pressure on all wetted
components. A small continuous flow of nitrogen is required, however, to protect the turbine
and deaerator tank (if furnished).
Step 5 – Wet Layup with Nitrogen Cap (HRSG Water Touched Circuits and Feedwater)
In accordance with the second guiding principle, a nitrogen cap of 5 psi (about 35 kPa) is
maintained over wetted economizer and evaporator circuits of the HRSG and the feedwater
system. The pH of the water may be raised with ammonia (at concentrations of up to 10 ppm) for
longer wet layup periods. Ammonia addition may be made during the shutdown if a long layup is
3-8
expected. If not known before shutdown, draining and refilling will be required; the operation
should be done under positive nitrogen pressure and deoxygenated fill water should be used.
This approach should also be followed if it becomes necessary to drain these components for any
reason.
Periodic (at least weekly) circulation of the wet layup solution is needed to help avoid pitting
corrosion. In HRSG designs with circulation pumps, this pump can be used to provide
circulation. Another approach is the use external pumps that permit continuous circulation of
water in the HRSG circuits during shutdowns.
Step 6 – Wet Layup with Nitrogen Cap (Balance of Cycle)
As the turbine spins down, nitrogen is added to the condenser, which also purges the reheater
system. A continuous purge of nitrogen is necessary to account for leakage through the turbine
steam seals.
Nitrogen is added to the external deaerator and storage tank (in systems equipped with them)
while this system is still hot. A small flow of nitrogen is provided to purge this system.
A nitrogen cap is maintained on the shell side of any feedwater heaters provided.
Step 7 – Wet Layup for Longterm and Extended Shutdowns
When using wet layup for longer storage periods, additional steps can be taken to protect the
HRSG steam touched circuits. For longterm shutdowns superheater circuits may be filled with a
solution of deoxygenated high purity water treated with (up to 10 ppm of) ammonia and a
nitrogen cap is maintained. For extended shutdowns reheater circuits (when present) are isolated
from the turbine and filled with a solution of deoxygenated high purity water treated with (up to
10 ppm of ammonia) and capped with nitrogen. Protection in this way is consistent with the
second guiding principle of keeping the water from becoming saturated with oxygen. It is very
important that the fill water used is deoxygenated (Appendix B) and that a means of reliable
circulation should be provided as well.
Step 8 – Equipment Inspection and Maintenance
Equipment inspection and maintenance activity could be needed while the unit is in an
intermediate, longterm or extended shutdown. The approach to be followed is dependent on the
type of layup in use.
Access for maintenance is relatively simple when employing dehumidified air for dry layup
(Step 3). The atmosphere present is safe though applicable procedures for confined space entry
and general safety should be followed. Corrosion protection will continue so long as the relative
humidity remains low. Thus it is advantageous to minimize the time equipment is exposed to the
ambient environment. The dehumidification equipment can be left in place and in operation if
this will not interfere with planned inspection and maintenance activities.
3-9
Care must be taken when the system is laid up dry with nitrogen (Step 4). The nitrogen
atmosphere must be thoroughly purged with air to provide an environment suitable for entry of
personnel. Since nitrogen gas does not support human life, it is extremely important that
nitrogen be completely displaced by air. The atmosphere within the equipment requiring
maintenance should be tested with suitable test equipment to ensure the equipment is safe for
personnel entry. All other relevant plant safety precautions that apply should be followed.
Further discussion is included in Section 3.3.3.
Whenever a component laid up wet (Step 5) requires inspection and maintenance, other system
components should be maintained in the wet layup condition. Nitrogen feed should be secured
and the component drained under atmospheric pressure. Entry for inspection and maintenance, in
accordance with relevant plant procedures is then possible.
The layup condition should be reestablished as soon as possible after work is complete unless the
unit will be returned to service.
3.3 Layup Protection Considerations Using Nitrogen
Shutdown periods should be viewed as a continuation of the good practices used during normal
operation. The shutdown period is a prelude to the layup of the unit. Layup procedures are
determined by the guiding principles for equipment protection (Section 2.3) and the duration of
the shutdown (Section 2.4). Nitrogen blanketing serves an essential purpose in preventing
oxygen ingress during layup.
Nitrogen blanketing is an especially significant topic, since it plays an important role in the
control of corrosion in combined cycle power plants. Nitrogen may be used either to cap
components that are to be maintained wet or for dry protection when applied to purge and
blanket systems as they drain to prevent the entry of ambient air. In order to produce an
effective nitrogen cap or blanket for oxygen exclusion from combined cycle generating unit
components, both the appropriate nitrogen supply/delivery system and the appropriate
application procedures are required. The final key to success is to follow the established
procedures implicitly at the time the application is needed.
3.3.1 Nitrogen System Design and Operation
Combined cycle plant designers are frequently asked to include nitrogen systems as part of the
plant design and the HRSG manufacturers generally include suitable points of connection for
nitrogen capping or purging of their equipment. Important system design characteristics are
generally common to all steam-water cycles and may be summarized as follows.
• Multiple connection points must be available to allow capping of any components or HRSG
circuit to be maintained wet.
• Nitrogen system flow rates and capacity should be satisfactory for intended use.
3-10
• For nitrogen purging (draining under nitrogen) procedures, the flow rate should be sufficient
to match drain rates while maintaining positive pressure so as to continually exclude air
ingress.
• System capacity should be sufficient to meet anticipated requirements for use, meaning there
should be enough capacity to minimize the risk of consuming all nitrogen consistent with
intended operating procedures and monitoring practices. This should be considered carefully
in units expected to operate in the peaking mode.
• The system must be designed in accordance with all applicable codes and standards.
Where nitrogen is to be introduced to high pressure vessels and components, double isolation
valves with check valves are typically utilized. Some users choose to also provide quick-
disconnect connections between the nitrogen source and the component isolation valves. This is
to avoid inadvertent introduction of nitrogen to equipment when it is not desired. Such an
arrangement enhances personnel safety and takes virtually no longer to activate and secure than a
hard piped system.(7)
Nitrogen source and purity are important design factors deserving of careful consideration. As
the purpose of applying nitrogen is to exclude the ingress of oxygen from ambient air (second
guiding principle) the purity is very important. Whether purchased from a supplier or produced
on site, nitrogen will contain low levels of oxygen. With effective use of high purity nitrogen, the
probability of downtime corrosion is essentially eliminated. Purity levels of at least 99.5% are
considered suitable for plant use.(6) Higher purity nitrogen (99.9% and greater) is possible and
desirable as this will serve to minimize corrosion during shutdown.
There are three primary methods of obtaining nitrogen. Each has unique advantages and
disadvantages. Equipment required with each supply option can be purchased or leased,
depending upon which best suits the needs of plant personnel.
High pressure compressed gas storage is perhaps the most costly method; for this reason it is
probably not desirable if frequent usage is expected. These systems are simple to operate and
require relatively low inspection and maintenance.
Cryogenic liquid nitrogen storage systems are less expensive than compressed gas storage,
require less frequent replacement than compressed gas storage vessels and can provide a high
purity gas. The systems are simple and reliable to operate. The major drawback to the cryogenic
storage system is if the system is used infrequently. Some nitrogen is continually lost each day
due to pressure relief resulting from vaporization of liquid nitrogen due to accumulation of heat
from the surrounding environment.
On-site production with membrane separation equipment is the third method of obtaining
nitrogen for equipment protection. Although potentially least expensive, the purity of gas
resulting from on-site generation is dependent on design and operating conditions. With on-site
nitrogen generation systems, the rate of gas production affects the resulting purity: the faster the
production, the lower the purity. In order to achieve an effective blanket by this method,
component drain times might need to be very long if the system is not specified and designed to
meet the expected operating conditions. These systems are more complicated and require more
3-11
operator and maintenance attention than the other options. On-site nitrogen production
equipment can be either purchased or leased. If purchased, a contract for inspection and/or
maintenance is necessary if this expertise is not located within the organization.
3.3.2 Application of Nitrogen
In order to provide the desired protection, nitrogen blanketing system must not only be well
designed; they also must be properly operated. Procedural errors during application of nitrogen
can allow corrosion to develop. Comprehensive operating procedures should be developed for
the nitrogen system to cover all situations. For example, the application of a nitrogen cap to
various pressurized HRSG circuits and possibly other components should consider the fact that
gas must be applied before the pressure has decayed to atmospheric. Use of nitrogen to purge
any components under vacuum requires a higher priority and should be done earlier in the
shutdown. Thus the needs of the unit during each shutdown must be considered in the context of
the protection strategy to be implemented and associated needs for nitrogen. Key actions needed
here include:
• Select which parts of the system will be protected with nitrogen and how nitrogen will be
applied (for wet or dry protection).
• Establish a hook-up and valve list which will accommodate this.
• Select an order in which systems will be placed in the layup condition.
• Construct a short sequential procedure that follows this order.
• Delineate the system conditions that should exist for starting to apply nitrogen to each part of
the system.
• Train personnel on the procedure and included equipment.
Application of nitrogen to areas of use should start consistent with the unit shutdown procedures
and anticipated outage activities. When required, application of nitrogen to steam touched
components should begin with the HRSG circuits while the metal temperatures are still above the
saturation temperature of the steam. Once purging is complete, isolate the circuit and maintain a
slight positive nitrogen pressure on superheaters or slight flow of nitrogen through reheater
circuits that are not isolatable. This is followed by purging of the main steam piping and the
steam turbine, followed by the condenser shell as shutdown proceeds. As a consequence of shaft
seal losses, the turbine will continually lose nitrogen to the atmosphere. Thus a slight flow of gas
sufficient to maintain a slight positive pressure is necessary when using nitrogen to protect the
system. Otherwise, the system could be subject to ingress of air containing oxygen and moisture.
On the other hand, over pressurization can interfere with the performance of the rupture disks.
3.3.3 Plant Maintenance
Signs should be posted at all potential points of entry into confined spaces indicating that a
nitrogen atmosphere might be or is present and that equipment entry is prohibited until
appropriate oxygen recovery procedures have been performed on such component. If confined
3-12
space entry becomes necessary once the blanket is in place, filling the desired system with water
and then draining under air usually will effectively render the component safe to enter. However
it is always prudent to follow all plant safety procedures and monitor the atmosphere prior to
entry even after draining under air.
A pure nitrogen atmosphere is very dangerous and potentially lethal as oxygen is necessary to
sustain human life. In an oxygen-deficient atmosphere, unconsciousness is almost instantaneous,
with death ensuing within minutes. Some organizations have elected to ban the use of nitrogen
purging due to safety concerns. Therefore, when nitrogen is in use it must be emphasized that
extreme caution is exercised in making equipment inspections if such equipment can be or has
been blanketed with nitrogen. By planning when inspections are to be accomplished and by
testing the atmosphere before and during the inspections, such operations can be completed
safely. Development of appropriate procedures coupled with strict adherence to these procedures
for entry into potentially blanketed confined spaces will result in a safe nitrogen blanketing
operation.
Whenever inspection and maintenance work has to be accomplished from within the nitrogen
blanketed confined space, then caution, as described above, must be practiced. If the work is to
be done on the blanketed equipment from the surrounding environment, the work can proceed as
normal. With the low pressure used for the blanket, nitrogen losses from any openings in the
equipment to non-confined spaces will be insufficient to alter the oxygen concentration in the
immediate area. If welding needs to be accomplished, the blanket pressure can be removed
temporarily to make the initial welds, and then reapplied with very little loss of integrity of the
blanket and corrosion protection, even in that local area. If work needs to be done from the
combustion gas side of the HRSG, confined space procedures should be followed. Cracking open
of the fan dampers will allow sufficient air flow as needed to correct and prevent any oxygen
dilution even close to tube leak locations. Appropriate planning and procedures can allow for
work to be accomplished on the blanketed equipment in many cases.
3.4 Considerations for Dry Layup Protection with Warm, Dehumidified Air
It has long been known that corrosion of metals is dependent on the environment in general.
Investigations of atmospheric corrosion clearly demonstrated that corrosion of steel surfaces
increases with increasing humidity level and essentially ceases under low humidity conditions.
Justification for the use of dehumidified air to protect ferrous surfaces from corrosion is depicted
in Figure 3-2, which is a plot of corrosion rate vs. relative humidity of air. This plot is based on
early 20th century research but subsequent investigations have provided generally similar trends.
This figure illustrates that corrosion of steels can be largely mitigated by maintaining air in
contact with corrosion prone surfaces at a relative humidity of 60% or less. It is normally
suggested that a relative humidity of 40% or less be maintained. To provide a safety margin,
systems are normally designed and operated to maintain relative humidity at no more than 30-
35%. The design should include appropriate sensors to monitor humidity at appropriate
locations; readings can be used for manual or automatic control of the system.
3-13
The use of clean, dehumidified air to purge fossil plant equipment during idle periods is routinely
practiced worldwide. The mechanism of dehumidified air introduction, in combination with
effective draining and dying of steam and water touched surfaces, is elimination of residual
water and moisture as required by the second guiding principle for fossil equipment protection.
At higher humidity levels, any retained water can absorb oxygen; as this water is stagnant,
pitting corrosion will develop. Dehumidified air rapidly evaporates any residual water left after
draining. Also, condensation of moisture can occur on surfaces if the humidity is not sufficiently
low; this surface moisture can dissolve oxygen, which also allows pitting corrosion on the metal
surfaces.
Figure 3-2
Corrosion Rate of Steel Relative to Humidity of Air
Today, dehumidified air is widely used by industry for a variety of protection and preservation
purposes above and beyond corrosion control.(8) Equipment is available to provide the
environment needed to meet a variety of objectives.
3-14
3.4.1 Provision of Dehumidified Air
In an earlier EPRI report,(9) it was noted that in cases where the climate at the plant site is arid it
may not be necessary to produce dehumidified air. If the ambient air at the plant site is expected
to be consistently dry (with a relative humidity of less than 40%) during the shutdown period, the
ambient air could simply be circulated through the various systems to be protected at a nominal
cost. Of course such an approach is not possible at most sites and could be risky if the actual
humidity levels are higher than anticipated. However, the vast majority of plants need a suitable
dehumidification system to ensure that the air is sufficiently dry at all times. Historically, the
primary application of dehumidified air in power plants has been for extended protection of
equipment and plant mothballing applications.(10)
A schematic drawing of the desiccant dehumidifier design commonly used for dry layup of fossil
plant equipment is shown in Figure 3-3.(5,9) The dehumidifier consists of a wheel of ceramic
material that has been corrugated, so air can pass lengthwise down the fluted corrugations. A
desiccant is impregnated into the structure. Type 1 silica gel is the desiccant normally applied in
systems for power plants. Moisture is attracted from the air onto the desiccant as the air passes
through the wheel. Alternative dryer design arrangements such as multiple vertical bed systems
have been offered and still may be in use at some power plants but the rotary desiccant wheel is
most widely used and currently available from equipment suppliers.(11)
Figure 3-3
Rotary Desiccant Dehumidifier(5,9)
The wheel rotates slowly between two air streams (about one revolution every 10 minutes). The
first air stream, called the process air, is the ambient air dried by the desiccant for introduction to
the component or system to be protected. The air is also warmed as a consequence of
dehumidification; the temperature of the process air is dependent on the temperature of the inlet
air and the amount of moisture removed. The second air stream, known as reactivation air is
heated and runs through the wheel in the opposite direction of the process air. Reactivation air
3-15
transfers heat to the wheel, heating the desiccant to remove and carry away its moisture so the
desiccant can be reused to collect more moisture from the process air.
Other dehumidifier components include two fans, one each to pull the process and reactivation
air streams through the wheel, a drive motor to turn the wheel, and a heater to warm the
reactivation air stream so it can dry the desiccant. An electrical control panel coordinates the
operation of the fans, drive motor, and heater.
As shown in Figure 3-3, the humid inlet air and reactivation air must both be filtered to protect
the desiccant from blinding by airborne solids; however, filtration of the dehumidified process
air is not practiced in most applications as entry of desiccant to the system is rare. Gross losses of
desiccant, resulting from physical damage of equipment are possible but unlikely and losses due
to normal attrition of the desiccant media associated with thermal cycling during operation are
very minor. If desired, a system could be supplied with an outlet filter to provide further
assurance that the media will not be introduced to the steam turbine or other components. High
efficiency filters are available and sometimes included in systems where clean conditions are
desired.(11)
While automatic controls are available, most systems are manually controlled. The rotation speed
of the wheel is fixed; thus it is important to consider the allowable time for reduction of the
relative humidity to the desired level and drying out of any accumulations of water that may
occur during the shutdown of the unit. Operating economy during extended shutdown periods is
optimized by recirculation of dry air and intermittent (on-off) operation once the humidity level
has been reduced to that required for equipment protection. While losses of dry air due to leaks
are undesirable, they are unlikely to result in localized corrosion if the system provides sufficient
humidity monitoring capability. (11)
3.4.2 Protection in Combined Cycle Plants Using Dehumidified Air
Care must be taken in system design. While some organizations develop their own
specifications, many work with the design engineers of the equipment suppliers to assess the
specific needs of individual applications. For power generation applications, the allowable
relative humidity is the primary design criterion. Key aspects to consider include: (11)
• Areas of the cycle to be protected.
• Optimal point or points of access for air introduction and removal.
• System capacity required (note criteria for frequency of system air changes listed earlier).
• Performance requirements: for power station applications, reduction of relative humidity in
air exiting the system to 30% will provide reasonable flexibility and satisfactory protection.
• Placement of humidity sensors to monitor overall performance and ensure that any areas of
possible water accumulation are quickly dried out.
As indicated earlier, it is very important that full consideration be given to system draining
procedures so as to ensure insuring that there are no substantial pools or areas of free water;
3-16
otherwise oxygen pitting is a possibility at these locations until they are dry. Admission of warm
dehumidified air should begin as soon as practical and while surfaces are hot enough to quickly
evaporate surface moisture. Very rapid drying of steam turbine surfaces without moisture
accumulation is possible if the air is applied while the metal is still hot.(11)
Effective use of humidity sensors and, to the extent possible, recirculation of dry air exiting the
protected cycle components serves to quickly eliminate collection of water. Recirculation of dry
air also reduces system operating costs.
The power system components to be protected must be kept as air tight as possible. The dry air
circulation systems are then sized to provide adequate refreshment of dehumidified air to the
component to be protected. Typical rule of thumb values for sizing are as follows(10):
• Ten air changes per hour for all water/steam-side components, including steam turbines,
HRSG circuits, feedwater system components and condensers.
• One air change per hour for flue gas-side components.
• Five to ten air changes per hour for gas turbine components and generating equipment.
If the installation does not allow the systems to be air-tight, larger values are used. If the systems
are exceptionally tight, smaller values can be used, or only a portion of the circulating air can be
processed through the dehumidifier. In all cases, the objective is to quickly reduce the relative
humidity of the dry air to 30% or less and maintain it at these levels until the unit is to return to
service.
3.4.3 Applications of Protection with Dehumidified Air
Depending on circumstances, the following possible applications of dehumidified air protection

of water and steam touched surfaces are most likely at combined cycle plants:
• Protection of Steam Turbines and Other Steam Touched Surfaces
• Protection of the Entire Steam-Water Cycle
3.4.3.1 Protection of Steam Turbines and Other Steam Touched Surfaces
The need to protect the steam turbine alone is a simple application that may be needed at times
when other areas of the cycle are undergoing extensive maintenance, repair or refurbishment
activities that will require long outages. In such cases the turbine may need to be isolated from
the steam supply piping and/or the condenser.
An example of dry layup of a steam turbine in a fossil plant is shown in Figure 3-4.(12) It is
necessary to preclude any steam ingress into the laid up turbine by installing additional vents and
drains (with an 8 inch (200 mm) siphon). The turbine has to be equipped with additional
connection points for dry air or venting. In this case(12), two air changes per hour were sufficient
for the steam turbine and condenser. In another example of dry layup of another turbine, Figure
3-17
3-5 shows the values of temperature and air humidity when using two air dehumidifiers (1 with
1.1 kW and 1 with 5.4 kW).
A more common application would involve the use of dry air to protect the turbine and other
steam touched components. Protection under such a configuration could be useful for
intermediate as well as longterm and extended outages. The emphasis here would be on inclusion
of those steam touched components connected to the turbine that usually cannot be isolated
easily and thus also may not be easily or effectively purged with nitrogen. Examples include the
steam piping to the turbine, the reheater circuit (where part of the design) and the condenser
steam space. Care is needed to select the optimal points of dry air ingress and egress so as to
ensure that the system can be activated and secured easily as needed.
Figure 3-4
Dry Layup of 107 MW Turbine Showing Measured Values of Temperature and Air Humidity
With some designs it may be possible to keep the HRSG water touched circuits and the
feedwater system laid up wet with a nitrogen blanket and the steam turbine and selected steam
touched components laid up dry with warm dehumidified air. When considering any protection
approach it is necessary to keep the guiding principles in mind since areas protected by dry air
must avoid moisture (third principle) and areas protected wet must not be exposed to air and
oxygen (second principle). In such cases the hotwell should be drained with a nitrogen purge and
isolated. Superheater circuits, which should be reliably isolatable from the main steam line to the
turbine, could be drained (or laid up wet) and pressurized with nitrogen. Similarly, external
deaerators and storage tanks (where provided) could be laid up wet with a nitrogen cap.
3-18
Figure 3-5
Turbine: Dry Layup Using Dehumidified Air
3.4.3.2 Protection of the Entire Steam-Water Cycle
More widespread protection is possible but requires more comprehensive analysis of the system
to be protected so as to size the dry air system equipment properly. Attention must also be paid
to the procedures used to shut down the unit so as to maximize removal of water when draining.
Draining equipment when hot is necessary to maximize flashing of surface moisture. Experience
at a conventional plant(13) has shown that moving air through equipment that is still hot can
enhance the flashing and drying process; similar techniques could perhaps be developed and
applied to combined cycle systems. Special care should be taken in draining of line connections
that could still retain water after the major components have been drained. It is also important
that all areas to be protected are completely isolated from water source connections that are
pressurized during the shutdown.
For complete protection of combined cycle systems the likely points of dry air introduction and
removal would typically be the condenser hotwell and the discharge side of the condensate
pumps. Dehumidified air introduced to the condenser hotwell would pass through the steam
turbine, reheater circuits and associated piping would be able to enter the superheaters and water
touched circuits of the HRSG providing the turbine stop valves remain open. From there the dry
air would pass through the feedwater system components and back to the condenser hotwell.
The system and operating procedures utilized to supply dry air for protection of the entire cycle
must be customized to adapt to various heat cycle configurations. Many systems consist of two
or more multistage HRSGs providing steam to a single steam turbine. The system may also
include auxiliary steam connections. In complex systems, it is necessary to carefully consider all
operating contingencies and design the system operating procedures accordingly.
To illustrate the thought process needed to apply warm dry air, a schematic drawing for
combined cycle unit composed of a single HRSG with three drum type evaporator circuits
3-19
supplying steam to a turbine is considered as shown in Figure 3-6. One possible dry air
application flow path for the system as shown in the figure can be described as follows. Dry air
is discharged from the dehumidifier via a fan into the condenser and then flows through the low
pressure turbine continuing through the intermediate pressure turbine section to the reheater, the
high pressure turbine and the HRSG evaporator and economizer. Backward flow of warm dry air
(relative to flow of water and steam in service) continues through the preheater circuit (internal
to the HRSG in the figure) and the feedwater system. Dry air flows through the feedwater
system, which includes an external plate type heat exchanger (bypassed) and is returned to the
dehumidifier to remove moisture from the air.
Other areas of the system not all shown in the figure also can and should be protected with
dehumidified air. Dry air will also pass from the hotwell through the condensate pump inlet
piping and can be returned to the dehumidifier via the discharge check valves. Attemperation
lines and any extraction lines are left open so dry air can pass through them.
Figure 3-6
Protection of the Entire Steam-Water Cycle with Dehumidified Air
The preferred configuration is dependent on unit-specific isolation capabilities and ease of access
to suitable dry air ingress and egress points. The ability of commercially available systems to
effectively dry and circulate air must also be part of the assessment. Fan requirements and
capabilities must be evaluated carefully in complex systems. In all applications, a system capable
of reducing relative humidity of the air throughout the area being protected is the main
performance criterion.
3-20
In all applications, air moisture levels should be checked at the main air egress point. Humidity
sensor readings should be readily available to the operator. The humidity data should be used to
control system operation for economical operation. For example, it is possible to turn the
desiccant reactivation heater and blower equipment off when the relative humidity of returning
air decreases to a predetermined level, say 15-20% and turn them on when humidity increases,
say to >25%. Control can be either manual or automatic as desired. The extent of cycling
required is dependent on tightness of the system, extent of dry air recycling, and ambient air
humidity levels.
3.5 Comparison of Wet and Dry Layup Methods
An overall comparison of the operational advantages and disadvantages of wet and dry layup
methods indicated in the Figure 3-1 roadmap of Section 3.2 and discussed further in Sections 3.3
and 3.4 is given in Tables 3-1 to 3-3. The possible disadvantages have been successfully
overcome in other plants but should carefully be considered when developing procedures for
application to individual units. When considering and selecting layup procedures for a specific
HRSG and its related equipment, responsible personnel should always be cognizant of the
guiding principles for equipment protection as is emphasized throughout these guidelines. The
optimal operational chemistry treatment for the feedwater and each evaporator circuit should also
be kept in mind.
As discussed at length previously, EPRI research clearly indicates the importance of avoiding
loss of passivation of steam turbine surfaces during shutdown periods. For protection of the
turbine from loss of passivation, which can ultimately lead to damage by corrosion fatigue and
stress corrosion cracking, use of warm, dehumidified air is considered superior to other methods,
including nitrogen blanketing. To protect the turbine with nitrogen, a relatively large system is
required due to the seal losses; nitrogen systems sized to cap the wet circuits of the HRSG and
the feedwater system could be incapable of meeting the turbine protection requirement. Most of
the major steam turbine manufacturers now indicate maximum allowable time intervals after
which the turbine requires protection; these intervals range from about 2-7 days. Use of
dehumidified air is generally specified as the preferred method of protection.
3-21
Table 3-1
Shutdown and Layup Advantages and Disadvantages: Wet Layup
Wet Layup* with Nitrogen Cap

*Typically with ammonia only; reducing agents not allowed without copper in feedwater system
Advantages Disadvantages
1. No change in chemistry for short term shutdowns 1. Requires nitrogen cap be applied before air can
enter the system
2. Easily tested and maintained
2. Need to circulate and monitor wet layup
3. Can also be used for longer shutdowns solutions regularly
3. Should not be used when freezing is possible
4. System must be drained under air if entry is
required.
5. Refilling requires high purity water of low
dissolved oxygen content
6. Ammonia must not be added if copper or copper
alloys are present in the system
7. Tight isolation is needed to avoid leaks
8. If chemicals are added for longer shutdowns, it
may be necessary to drain, rinse and refill prior to
startup; also possible waste disposal concern
Table 3-2
Shutdown and Layup Advantages and Disadvantages: Nitrogen Blanketing
Nitrogen Blanketing
1. System need not be completely dry 1. Does not support life; use prohibited by some
organizations; requires air purge prior to entry
2. Protection independent of climatic conditions
2. Should be applied before air can enter
3. May also be used to cap normal operating fluid components to be protected
during short outages
3. Cost of nitrogen and distribution and control
equipment
4. Nitrogen pressure cannot be maintained if
system valves leak
5. Reheater normally cannot be isolated
3-22
Table 3-3
Shutdown and Layup Advantages and Disadvantages: Dehumidified Air
Dry Layup with Dehumidified Air
1. Utilizes ambient air 1. Drying equipment and blowers required and

consume power when used
2. No risk to personnel
2. Climatic conditions may influence storage
3. Residual heat in metal utilized for drying conditions; minimized in tight systems
4. Whole unit or individual components may be 3. Drying of surfaces should be maximized while
protected draining; even draining hot and under pressure
5. Independent of ambient temperature if air dry does not ensure immediate water removal though
enough any residual water or moisture eventually will be
removed by the dry air
6. Maintenance on plant performed without
problems 4. Time is required to activate, monitor and
deactivate the system
7. Easy monitoring
8. Tolerant of small system leaks
The near exclusive use of dehumidified air for protection of fossil cycle components including
those of combined cycles continues to be on an as required basis for extended or mothballing
protection, as may be needed for various reasons. Traditionally, such applications have involved
leasing of the equipment involved. Field experience has shown that it is generally possible to
bring the dehumidification equipment to the plant and conveniently position it and connect it to
the cycle at one or more locations as may be needed. Thus it should be possible to do so with
permanent systems where desired.
Further, the trend towards designing of combined cycle units for seasonal peaking service has
reportedly resulted in a few cases where the anticipated need for more frequent use of dry air,
such as for longterm and extended protection has been recognized and the requisite equipment
included in the design as a permanent system. Thus these newer units with permanent
dehumidification systems will be better positioned to provide protection of the turbine even
during intermediate term outages as is indicated to be desirable based on EPRI research and
generally recommended by the manufacturers.
For those plants not so equipped and subject to frequent intermediate term outages, consideration
should be given to provision of an on-site dehumidification system capable of protecting the
steam turbine. In most cases, it should be possible to engineer and size the system to protect the
steam turbine, any reheaters and associated steam touched piping. Provision of equipment
needed for dehumidified air protection of the entire cycle could still be leased on an as needed
basis if desired.
3-23
Layup method assessment should also consider the following unit-specific factors:(14)
• The nature and expected duration of the shutdown.
• The possibility the shutdown duration may be required for operation on short notice.
• Facilities available for proper disposal of layup solutions.
• The possibility of freezing conditions during shutdowns.
• The practicality of establishing and maintaining all the required conditions of a given
procedure with available resources.
• Local atmospheric conditions, e.g., salt air environment.
• The availability of sufficient high purity condensate, deaerated demineralized water, nitrogen
or dehumidified air during the unit outage.
Finally, it should be understood that to take no action with respect to protection of the steam
water cycle during shutdowns is an unacceptable choice as it will lead to off-line corrosion,
breakdown of protective oxide films and transport of iron oxides to the HRSG during startups. It
thus invites premature failures of HRSG tubing due to pitting attack. It also restricts the
advantages to be derived from proper selection and optimization of the operating cycle
chemistry.
3.6 Monitoring During Storage
An essential part of layup is to monitor the integrity of all systems for proper chemistry, loss of
pressure, loss of fluid or gases, and an adequate supply of dehumidified air or nitrogen.
Operation of manually controlled dehumidified air systems should be checked daily and the
relative humidity levels reviewed. Pressure gages should be monitored on a weekly basis to
verify the absence of leaks in the systems capped or blanketed with nitrogen.
All wet layup solutions should be circulated at least weekly to avoid development of stagnant
conditions and ensure good mixing of these solutions. During intermediate or longterm
shutdowns circulation should be followed by sampling, using sample connections which yield
representative samples of the layup solutions.
Additional chemicals should be added to replenish those that have deteriorated or lost by
leakage. Leaks should be detected promptly and repaired to prevent loss of chemicals and
nitrogen or dehumidified air.
3.7 Environmental Considerations
The disposal of layup solutions containing high concentrations of alkaline chemicals such as
ammonia, and/or high concentrations of reducing agents (only for units with AVT(R) feedwater
chemistry) such as hydrazine or hydrazine substitutes, poses potential problems from an
environmental standpoint. The solution to these potential problems may require modifications to
3-24
existing waste treatment facilities. The cooperation of regulatory authorities should be a part of
the investigative process necessary to resolve these environmental issues.
3.8 References
1. Delivering High Reliability Heat Recovery Steam Generators. EPRI, Palo Alto, CA: 2003.
1004240.
2. Heat Recovery Steam Generator Tube Failure Manual. EPRI, Palo Alto, CA: 2002.
1004503.
3. Guidelines for Controlling Flow-Accelerated Corrosion in Fossil and Combined Cycle
Plants. EPRI, Palo Alto, CA: 2005. 1008082.
4. Survey Results. Proceedings: Boiler Tube and HRSG Tube Failure and Inspection
International Conference: November 2-4, 2004, San Diego, California. EPRI, Palo Alto, CA:
2004. (Publication pending.)
5. Cycle Chemistry Guidelines for Combined Cycle/Heat Recovery Steam Generators (HRSGs).
2005. 1004925.
7. R. D. Wine, “Effective Nitrogen Blanketing of Power Generating Equipment for Oxygen
Exclusion and Corrosion Control”, Presented at the 21st Annual Electric Utility Chemistry
Workshop, University of Illinois, May 2001.
8. L. G. Harriman III, ed., The Dehumidification Handbook, Second Edition, Munters
Corporation, Amesbury, MA. 2002.
9. Sourcebook for Plant Layup and Equipment Preservation (Revision 1). EPRI, Palo Alto,
CA:1992. NP- 5106.
10. D. Kosar, “Power Plant Preservation Using Desiccant Dehumidifiers”, Proceedings: Fossil
Plant Layup and Reactivation Conference, EPRI, Palo Alto, CA: 1992. TR-101250.
11. J. Siemasko, Munters Corporation, personal communications with K. Shields, May and July
2005.
12. H. Steger, “Standby Corrosion Prevention in Power Plants” (in German). Der
Maschinenschaden, Vol. 49, No. 1, pp. 23-27, 1976.
13. M. E. Walker, “Passivation of Unit 3 State Line Station through Dehumidification”,
Proceedings: Fossil Plant Layup and Reactivation Conference, EPRI, Palo Alto, CA: 1992.
TR-101250.
14. The ASME Handbook on Water Technology for Thermal Power Systems, American Society of
Mechanical Engineers, New York, NY. 1989.
3-25
4
SHUTDOWN FOR VARIOUS CYCLE CHEMISTRIES
4.1 Shutdown Requirements for the Various Cycle Chemistries
Some of the design aspects of plants, which influence the establishment of shutdown procedures,
are outlined in a recent EPRI publication(1). They include operational aspects, such as steam
drum temperature, rate of cooling and pressure decay, and how these can be minimized and used
to maintain off-load conditions suitable for a fast restart.
Three guiding principles for chemical conditions given in Section 2.3 of this report, should be
used to minimize off-load corrosion. They may be summarized as follows:
i) Maintain the same potential (oxidizing/reducing conditions) for shutdown, layup and
startup as during normal operation, i.e., when using AVT(O) or OT, do not add a reducing
agent during shutdown. (Only when copper alloys are present in the feedwater system is it
appropriate to use AVT(R); during shutdown it is necessary to maintain reducing
conditions and keep air out.)
ii) Prevent the water from becoming oxygenated by preventing air ingress, by using nitrogen
or steam blanketing and avoid stagnant conditions.
iii) Keep water and moisture out of steam touched components by maintaining dry conditions
during shutdown by rapidly draining during shutdown and, if necessary, adding warm
dehumidified air to protect the steam turbine and reheaters.
An HRSG unit may consist of several pressure stages. These may all be operated using the same
method of chemical conditioning, e.g., AVT or OT. However, some may operate with a
combination of AVT or OT, and solid alkali added to the low pressure evaporator water. Others
could operate with different solid alkali concentrations in the various pressure stages. The
chemical conditions at shutdown and layup during short outages should be the same as expected
during normal operation. However, care is needed during startup to ensure that the chemical
conditions (e.g., PC or CT) in one pressure stage (e.g., LP) do not adversely affect the chemical
conditions in other pressure stages or other areas of the cycle, through the feedwater or due to
increased mechanical carryover.
Shutdowns may be needed for maintenance, either planned or unplanned, or for reasons of
economy. Chemistry excursions during service, if severe enough, can also require shutdown to
protect equipment from damage and possible failure. Such shutdowns typically require
inspection, maintemance and other actions before the unit is returned to service.
4-1
Shutdown for Various Cycle Chemistries
Chemistry variations from normal requiring unit shutdown are generally associated with
contamination of the steam-water cycle for various reasons. When the unit employs a water
cooled condenser condenser cooling water leakage is a possible and often significant source of
contamination. In combined cycle units the condener tube material is often titanium or, where
cooling water characteristics permit, stainless steel. Use of copper alloy tubing, typically more
prone to leaks over the operating life is less commonly used.
Timely detection and repair of condenser leaks during operation is critical to minimize potential
damage by harmful contaminants such as chlorides and sulfates. Impurities will concentrate in
drum evaporator circuits where they may cause corrosion. In once-through evaporator circuits,
impurities will enter the steam touched circuits and steam turbine. Condensate polishers can help
decrease the impacts of contaminant ingress on chemistry but are not commonly provided on
combined cycle units. Units without polishers experiencing condenser leaks, regardless of
cooling water chemistry characteristics, or subject to contamination from other sources generally
should be shut down to protect the evaporators and steam path components.
Protection of equipment is of importance during all shutdowns and methods to be applied should
be selected in consideration of the expected duration of the shutdown and the nature of any
inspection and maintenance required. Section 3 describes the available approaches that are
suitable for various situations.
As most combined cycles do not include copper in the feedwater system, oxidizing all volatile
treatment, AVT(O), is suitable for the majority of units, while a few may be able to operate
beneficially with oxygenated treatment (OT). Reducing agents should not be added in cycles
employing these feedwater treatments and ensuing discussions of shutdown reflect this. (Only
units with copper in the feedwater system should apply a reducing agent such as hydrazine to
establish reducing AVT conditions.)
The various methods of chemical conditioning are considered in the following sections in the
same order as they appear in the recently revised Cycle Chemistry Guidelines for Combined
Cycle/Heat Recovery Steam Generators (HRSGs)(2).
Since, in some cases, the circuits of multi-pressure HRSGs may operate on different cycle
chemistries and also may include both drum type and once-through circuits, operators should
consider all of the sections which follow that are relevant to the HRSG of interest, to ensure that
customized shutdown procedures developed comply with the guiding principles of Section 2.3,
as well as the requirements of Sections 4.2 to 4.7 which follow.
4.2 Phosphate Continuum Treatment for Drum HRSG Circuits
As described in the HRSG Cycle Chemistry(2) and phosphate guidelines(3), phosphate continuum
(PC) treatment was designed to cover a wide range of operating pressures and boiler
characteristics. Two sets of control curves were developed. Low levels of phosphate may be used
when there is only a need for low levels of protection from contamination in the evaporator
circuit. When the potential for contamination and thus the need for corrosion protection of the
evaporator circuits is greater, higher levels of phosphate may be applied; this is known as PC(H).
4-2
In high pressure evaporator circuits, it is very important to measure the carryover to verify that
the treatment will not contaminate the steam. At higher evaporator pressures operating at or
above 2000 psi (13.8 MPa) it is usually possible to use only PC(L). However, In some HRSG
designs, it may be possible to use PC(H) in the low pressure and intermediate pressure circuits
while using PC(L) in the high pressure evaporator circuits.
The pH and the phosphate concentration of each circuit treated with PC should be monitored
closely when a unit trips. A sudden release of phosphate (hideout return) may indicate that the
phosphate concentration used during normal operation is too high. As a rule, any phosphate
hideout return causes a pH increase in the evaporator water.
During shutdown, the pH may also increase as the result of the phosphate hideout return. The pH
should be maintained within the selected control range even during shutdown. If necessary,
sodium hydroxide can be added to drive the pH into the acceptable range to protect the HRSG.
A road map for shutdown of HRSG evaporator circuits employing phosphate continuum (PC)
chemistry is presented in Figure 4-1. Shutdown should be closely related to layup, which in turn,
depends on the anticipated outage length. Based upon this road map, shutdown should proceed in
the following manner.
Figure 4-1
Road Map for Shutdown of Combined Cycle Units with Drum Type Evaporator HRSG
Circuits Using Phosphate Continuum (PC) Chemistry
4-3
The road map for shutdown for phosphate continuum units, Figure 4-1, should be used in
conjunction with Figure 3-1 in Section 3.2.
Figure 4-1 can be divided into four steps.
Step 1 – Normal Cycling or Peaking: Load Reduction or Shutdown
Normal cycling or peaking load reduction or shutdown presumes a short term shutdown and use
of protection measures as described in Section 3.2 and Step 1 of the Figure 3-1 road map.
An orderly reduction of load can be performed for routine cycling operations. Also, an orderly
reduction of load or unit shutdown can be performed when contamination is minimal, as
determined by chemical monitoring during such transients.
During orderly load reductions, the cycle chemical limits for evaporator water should be adjusted
to conform with the phosphate continuum chemistry guidelines(2, 3) in use, PC(L) or PC(H) as
applicable. (Layup procedures are covered in Section 3.2 of this document.)
Particular care should be exercised to monitor unit conditions (temperatures and pressures plus
condenser vacuum) during the shutdown so as to prevent air ingress; action should be taken to
provide another form of protection before this occurs. Blowdown should be maintained at an
appropriate level to remove contaminants from the system.
During shutdown, any indication of phosphate hideout return (increased levels of phosphate,
change of pH, etc.) indicates that the evaporator has not been operating at the optimum level
during normal operation. This should be corrected during normal operation by following the
procedure given in the HRSG Cycle Chemistry(2) and phosphate guidelines(3) to determine the
optimum level of phosphate.
Step 2 – Other Shutdowns
Duration of planned or unplanned outages will depend on system demand or the extent of the
work required before returning the unit to operation. These shutdowns typically require
intermediate, longterm or extended protection. The length of time required for maintenance must
be estimated and, depending on this estimate, an appropriate layup should be initiated. For longer
wet layups, adjustment of chemistry prior to shutdown may be desirable. See Section 3.2
discussion and the Figure 3-1 road map.
An unplanned shutdown caused by chemistry upsets (additional shutdown requirements are

discussed in Steps 3 and 4) and outages due to an equipment or system failure can be treated as
for a planned outage.
Step 3 – Chemical Transients: Condenser Leakage
The level of contamination in the cycle is dependent on both the amount of cooling water ingress
(size and number of leaks) and, usually more importantly, the cooling water dissolved solids
4-4
concentration. Evaporator water pH control is critical and monitoring condensate cation

conductivity and sodium levels will assist in estimating the magnitude of the leak. The addition
of extra trisodium phosphate or 1-2 ppm of sodium hydroxide may be required, if the evaporator
water pH drops. Immediate shutdown of the unit is required if the evaporator water pH falls
below 8.
Chemistry monitoring is especially important when a condenser leak is suspected to be

developing and the cooling water is a high solids water such seawater, brackish water or high
solids cooling tower water. Without condensate polishing (as is usually the case), evaporator
water pH is impossible to control in such cases and immediate shutdown is required because,
with continued operation, serious damage can occur to evaporator tubes within a short period of
time.
On units with condensate polishing, there is greater flexibility in dealing with leaks that do not
rapidly depress the evaporator pH to levels requiring immediate shutdown; unit shutdown can
generally be accomplished in a more orderly fashion.
For small condenser leaks in units using fresh, relatively low dissolved solids cooling water, it
may be possible to avoid shutdown when the HRSG consists of drum evaporator circuits only;
however a load reduction would be needed. Avoidance of shutdown requires: effective chemistry
instrumentation to identify the leak promptly; the ability to rapidly and effectively isolate the
area of the condenser experiencing leakage (divided waterbox design): and reliable identification
and plugging of all leaks. It cannot be overemphasized that such action will be successful only if
rapid leak detection results in immediate action to reduce load and isolate the condenser.
Evaporator chemistry must be watched very closely if in-service assessment and repairs are
attempted; it may be necessary to take actions such as reducing pressure, blowing down and
addition of extra trisodium phosphate or sodium hydroxide to the evaporator. If evaporator
chemistry cannot be controlled, the unit should be shut down promptly, and the leaks isolated
and repaired.
Generally, the unit should be shut down to repair the condenser leak.
Substantial intrusion of any cooling water, such as may follow mechanical damage of several
tubes within the condenser, into the HRSG will require that the unit be shut down immediately. It
should then be drained, flushed and refilled with condensate quality water plus chemicals
consistent with operating requirements of PC treatment.
Step 4 – Chemical Transients: Chemical Intrusion
Some of the many possible causes of chemical intrusion (in addition to condenser leakage)
include:
• Makeup water system malfunction
• Chemical cleaning residue; acid, caustic, other
• Maintenance chemicals and preservatives
4-5
Minor chemical intrusions can be controlled by increasing evaporator circuit blowdown.
More serious chemical intrusions may require adjustment of evaporator water pH through
addition of more trisodium phosphate or 1-2 ppm of sodium hydroxide. If these treatments are
unsuccessful, the unit must be shut down if the pH falls below 8.0(2). The unit then requires
careful inspection to determine possible damage, and the necessity for repair and possible
chemical cleaning prior to restart.
Intrusion of chemical contamination requires immediate unit shutdown, draining and flushing the
unit. Inspection of critical areas of the system (evaporator circuits, superheater, turbine, etc.)
should be performed to assess the effects of chemical intrusion on the system. Chemical cleaning
of the affected components may be required depending upon the results of the inspection.
Equipment repairs may also be required. In such case, a longterm layup will be required (see
Section 3.2).
During emergency shutdowns, such as for major condenser leaks and extensive chemical
contamination, immediate unit shutdown is required. Therefore, little can be done to adjust cycle
chemistry during shutdown, since rapid action is required. During such occasions, the unit should
be drained, flushed and inspected to assess damages, as outlined previously. Restarting the unit
will be contingent upon this inspection, as will layup provisions.
4.3 All Volatile Treatment for Drum HRSG Circuits
General information on shutdown and layup protection for various planned shutdown conditions
is given in Section 3. Selection of protection measures should consider the governing guiding
principles of Section 3.2.
Unplanned shutdowns also occur and, by their very nature, are unpredictable. Evaporator circuits
employing all volatile treatment (AVT) have no corrosion protection. Contaminated feedwater
entering such circuits will generally result in corrosive and usually low pH conditions. Damage
and failure of evaporator tubing will occur unless prompt action is taken. This normally requires
shutdown of the unit and addition of solids based treatment chemicals (trisodium phosphate,
sodium hydroxide) to the evaporator circuits.
A road map showing a scheme for shutdown of a drum type HRSG with an all-ferrous feedwater
heating system operating with AVT is given in Figure 4-2. The time taken to achieve stable
shutdown conditions will be plant dependent. This should be determined for each unit, used as
guidance for future operations and amended in the light of operating experience.
4-6
Figure 4-2
Circuits using All Volatile Treatment (AVT)
The road map for shutdown of a drum-type HRSG unit operating on AVT with an all-ferrous
cycle, Figure 4-2, can be divided into four steps.
The steps are essentially similar to those described for PC (Section 4.2). In drum type HRSG
circuits operating on AVT, blowdown can be used for control of the evaporator water purity for
control of silica and, in the absence of contamination, other impurities that enter and concentrate
in the circuit.
4-7
During orderly load reductions, the feedwater and evaporator water chemical limits should be
adjusted to conform with the HRSG Cycle Chemistry(2) for drum evaporator units and the latest
AVT Chemistry Guidelines.(4).
Step 2 – Outages
work required before returning the unit to operation. The length of time required for maintenance
must be estimated and, depending on this estimate, an appropriate layup should be initiated. For
longer wet layups, adjustment of chemistry prior to shutdown may be desirable. See Section 3.2
discussion and Figure 3-1.
An unplanned outage due to an equipment or system failure can be treated as for a planned
outage.
Step 3 – Chemical Transients: Condenser Leak
conductivity and sodium levels will assist in estimating the magnitude of the leak.
In drum type evaporator circuits using AVT chemistry, the pH will begin to fall almost
immediately, often serving as the first indication of contamination. Immediate shutdown of the
unit is required if the evaporator water pH falls below 8. Addition of trisodium phosphate or
sodium hydroxide will help minimize corrosion damage.

time. Even leaks of low solids cooling water will usually depress the pH and thus require
immediate shutdown of the unit.
On units with condensate polishing, there is greater flexibility in dealing with small leaks that do
not rapidly depress the evaporator pH to levels requiring immediate shutdown. Also, unit
shutdown can generally be accomplished in a more orderly fashion.
4-8
Substantial intrusion of any cooling water, such as may follow mechanical damage within the
condenser, into the HRSG will require that the unit be shut down immediately. It should then be
drained, flushed and refilled with condensate quality water plus chemicals consistent with
operating requirements of AVT chemistry.
Some of the many causes of chemical intrusion (in addition to condenser leakage) include:
Minor chemical intrusions can be controlled by increasing evaporator blowdown.
More serious chemical intrusions may affect (lower) the evaporator circuit pH, necessitating
adjustment of pH through the addition of trisodium phosphate or 1-2 ppm sodium hydroxide (see
Sections 4.2 and 4.5). If these treatments are unsuccessful, the unit must be shut down (orderly
with polishers, immediately without polishers) if the pH falls below 8(2). The unit then requires
careful inspection to determine possible damage, and the necessity for repair and possible
chemical cleaning prior to restart.
Intrusion of chemical contamination often requires immediate unit shutdown, draining and
flushing the unit. Inspection of critical areas of the system (evaporator circuits, superheater
circuits, turbine, etc.) should be performed to assess the effects of the chemical intrusion.
Chemical cleaning may be required, depending on the results of the inspection. Equipment
repairs may be required. In such case, a longterm layup will be required (See Section 3.2).
During emergency shutdowns, such as for major sea water leaks and extensive chemical
be drained, flushed and inspected to assess damage, as outlined previously. Restarting the unit
4.4 All Volatile Treatment for Once-Through HRSG Circuits
Only a limited number of HRSGs include once-through evaporator circuits; in many cases, the
feedwater to this circuit is provided by a low pressure evaporator. The design includes a
condensate polisher or filter in some but not all cases; this equipment, when present, may only be
sized to handle full flow during startup of the unit.
4-9
Information is given in Section 3.2 (see Figure 3-1) and below for various planned shutdown
conditions. Unplanned shutdowns also occur and, by their very nature, are unpredictable.
Chemical contaminants entering once-through evaporator circuits will also enter the steam path;
prompt shutdown is required to prevent deposition and corrosion in superheater and reheater
circuits as well as steam turbines. Protection of the turbine is vitally important following such
events.
A road map for shutdown of a HRSG with a once-through evaporator circuit operating with
AVT(O) is given in Figure 4-3. The time taken to achieve stable shutdown conditions will be
plant dependent. This should be determined for each unit, as guidance for subsequent shutdowns
and amended in the light of operating experience.
The road map for shutdown of once-through HRSG units operating on AVT(O), Figure 4-3, can
be divided into four steps.
Figure 4-3
Road Map for Shutdown of Combined Cycle Units with Once-Through Evaporator HRSG
Circuits using All Volatile Treatment (AVT)
The steps are essentially similar to those described in Section 4.3 for units with drum type
evaporators, except that for once-through circuits, very high purity water is required for the
evaporator, as well as the feedwater (and steam), and control of the evaporator water purity can
not be achieved by blowdown.
4-10
Step 2 – Shutdowns
outage.
In once-through evaporator circuits, concentration of solids will not occur; some deposition is
possible but steam path contamination and resultant damage is of greater concern. Thus the
correct response action upon identification of condenser leakage is to shut the unit down to repair
the leak.
With condensate polishing, the unit can generally be shut down in a more orderly fashion.
However, most units with once-through evaporators have no or only partial flow polishing
capability.
Depending on an evaluation of the cycle chemistry, shutdown should be immediate or orderly, as

outlined above.
Substantial intrusion of cooling water into the HRSG will require that the unit is drained and
refilled with condensate quality water meeting the HRSG Cycle Chemistry Guidelines(2) for
once-through units operating on AVT.
4-11
Minor chemical intrusions can be controlled by employment of idle condensate polishers, if

available. Otherwise, immediate shutdown of the unit is required to protect the once through
evaporator circuit and all steam touched components.
Shutdown should be followed by draining and flushing the unit. Inspection of critical areas of the
system (evaporator circuits, superheater, turbine, etc.) should be performed to assess the effects
of chemical intrusion on the system. Chemical cleaning of the affected components may be
required, depending on the results of the inspection. Equipment repairs may be required. In such
case, a longterm layup will be required. (See discussion in Section 3.2.)
During emergency shutdowns such as for major cooling water leaks and extensive chemical
4.5 Caustic Treatment for Drum HRSG Circuits
Use of caustic treatment (CT) in drum type evaporators provides protection against feedwater
contamination. In high pressure evaporator circuits, it is very important to measure the carryover
to verify that the treatment will not contaminate the steam. Caustic is very corrosive to turbines
and steam purity must be monitored carefully, as described in the HRSG Cycle Chemistry(2)
guidelines.
Sodium hydroxide does not normally exhibit hideout and return properties as is often observed
when using PC. No adjustment in the evaporator chemistry is needed prior to short term
shutdown. As stated in earlier sections of this report, the preferred practice shut down with the
optimum operating chemistry. Feedwater pH should be kept in limits with addition of ammonia.
During short term shutdown, the unit should be bottled up under a nitrogen cap or pressurized by
with auxiliary steam. Performed properly, this will minimize air intrusion effects, including pH
depression by carbon dioxide. Long shutdowns require protection by one of the methods
indicated in Section 3.
The basic considerations outlined in Sections 4.2 and 4.3 for PC and AVT also apply during
shutdown for evaporator circuits using caustic treatment (CT), with the addition that special care
has to be taken to prevent any carryover of sodium hydroxide from the evaporator water, as this
could lead to stress corrosion of austenitic components in the steam circuits.
A road map for shutdown of a drum HRSG unit with an all-ferrous feedwater heating system
operation with CT is given in Figure 4-4. The time taken to achieve stable shutdown conditions
will be plant dependent. This should be determined for each unit, used as guidance for
subsequent repeat operations and amended in the light of operating experience. The road map
can be divided into five steps.
4-12
Figure 4-4
Circuits using Caustic Treatment (CT)
The steps are essentially similar to those described for AVT (Section 4.3).
During orderly load reductions, the feedwater and evaporator water chemical limits should be
adjusted to conform with the HRSG Cycle Chemistry Guidelines(2) and for drum evaporator units
and the latest CT Guidelines.(3)
4-13
Step 2 – Outages
outage.
conductivity and sodium levels will assist in estimating the magnitude of the leak. The addition
of extra sodium hydroxide may be required, if the evaporator water pH drops. Immediate
shutdown of the unit is required if the evaporator water pH falls below 8.

time.
On units with condensate polishing, there is greater flexibility in dealing with leaks that do not
rapidly depress the evaporator pH to levels requiring immediate shutdown; unit shutdown can
generally be accomplished in a more orderly fashion.
For small condenser leaks in units using fresh, relatively low dissolved solids cooling water, it
may be possible to avoid shutdown when the HRSG consists of drum evaporator circuits only;
however a load reduction would be needed. Avoidance of shutdown requires: effective chemistry
instrumentation to identify the leak promptly; the ability to rapidly and effectively isolate the
area of the condenser experiencing leakage (divided waterbox design); and reliable identification
and plugging of all leaking tubes. It cannot be overemphasized that such action will be successful
only if rapid leak detection results in immediate action to reduce load and isolate the condenser.
Evaporator chemistry must be watched very closely if in-service assessment and repairs are
attempted; it may be necessary to take actions such as reducing pressure, blowing down and
addition of extra sodium hydroxide to the evaporator water. If evaporator chemistry cannot be
controlled, the unit should be shut down promptly, and the leaks isolated and repaired.
4-14
Generally, the unit should be shut down to repair the condenser leak.
Substantial intrusion of any cooling water, such as may follow mechanical damage of several
tubes within the condenser, into the HRSG will require that the unit be shut down immediately. It
should then be drained, flushed and refilled with condensate quality water plus chemicals
consistent with operating requirements of CT chemistry.
Minor chemical intrusions can be controlled by increasing evaporator blowdown.
More serious chemical intrusions may affect (lower) the evaporator circuit pH, necessitating
adjustment of pH through the addition of a further 1-2 ppm of sodium hydroxide. If these
treatments are unsuccessful, the unit must be shut down if the pH falls below 8(2). The unit then
requires careful inspection to determine possible damage, and the necessity for repair and
possible chemical cleaning prior to restart.
Intrusion of chemical contamination requires immediate unit shutdown, draining and flushing the
unit. Inspection of critical areas of the system (evaporator circuits, superheater, turbine, etc.)
should be performed to assess the effects of the chemical intrusion. Chemical cleaning may be
required, depending on the results of the inspection. Equipment repairs may be required. In such
case, a longterm layup will be required (See Section 3.2).
4.6 Oxygenated Treatment For Drum HRSG Circuits
With oxygenated treatment (OT), careful control of the cation conductivity of the feedwater and
evaporator water is required. (5) Increases in the cation conductivity in the presence of oxygen
can result in corrosive conditions, and thus require immediate attention. Thus, consistent with
practice in conventional boilers using OT, it is necessary to stop oxygen feed at least one hour
prior to shutdown. Depending on the expected duration of the shutdown, the pH may also be
adjusted through addition of ammonia. These actions, in combination with any needed changes
in unit operation result in AVT chemistry conditions in the cycle. The only exception is that the
pH need not be increased for short term shutdowns.
4-15
As with drum type evaporator circuits treated with AVT, blowdown is available to control
concentrations of the low levels of impurities normally present; however, when feedwater
contamination enters the evaporator, there is no corrosion protection and the pH will fall rapidly.
In drum type evaporator circuits using OT chemistry, the pH will begin to fall almost
immediately, often serving as the first indication of contamination. Immediate shutdown of the
unit is required if the evaporator water pH falls below 8. Addition of trisodium phosphate or
sodium hydroxide will help minimize corrosion damage.
Short term shutdown guidance for OT(5) consists of stopping oxygen feed at least one hour
before shutdown of the unit. Deaerator vents, if furnished, should be opened, and venting
increased to aid in cycle deaeration in conjunction with stopping oxygen feed. Shutdown of
ammonia feed occurs simultaneously with unit shutdown.
Intermediate, longterm and extended shutdown guidance(5) consists of stopping oxygen feed at
least one hour before shutdown of the unit and of increasing ammonia feed rates.
Simultaneously, the deaerator vents, if furnished, should be opened or the deaerator venting
should be increased to aid in cycle deaeration in conjunction with stopping oxygen feed. The
object of the increase in ammonia feed rates is to achieve a pH higher than 9.0 in the HRSG
evaporator water (downcomer) of all individual circuits.
In other respects, the shutdown is essentially the same as outlined in the road map for a drum
evaporator circuit operated on AVT Figure 4-4, as discussed in Section 4.3.
4.6.1 Shutdown Procedures
Hydrazine and other reducing agents should never be utilized in HRSG circuits operating on OT.
The first guiding principle (see Section 2.3), clearly indicates that adding such treatments at
shutdown or during layup is inadvisable, as such action would change the potential of the water.
The preferred practice is to stop the oxygen feed at least one hour before shutdown and, for
longterm and extended shutdowns, to increase the pH in the cycle. Oxygen addition must be
stopped for all types of shutdowns. In order to exclude the possibility of oxygen in-leakage into
the shutdown unit by way of leaking valves, a physical disconnection of the oxygen supply from
the oxygen dosing line is advised.
4.6.2 Short Term Shutdown
Figure 4-5 graphically depicts guidance for short term shutdown. The guidance(5) consists simply
of stopping oxygen feed at least one hour before shutdown of the unit. Deaerator vents (if
furnished) should be opened, to aid in cycle deaeration in conjunction with stopping oxygen
feed. At the same time, any feedwater heaters (if furnished) should be carefully vented.
Shutdown of ammonia feed should occur simultaneously with unit shutdown.
4-16
Figure 4-5
Shutdown Chemistry Guidance for Drum Type Evaporator Circuits using OT Chemistry:
Short Term Shutdowns
4.6.3 Intermediate, Longterm and Extended Shutdown
Figure 4-6 graphically depicts guidance for longterm and extended shutdown. The guidance(5)
consists of stopping oxygen feed at least one hour before shutdown of the unit and of increasing
ammonia feed rates. Simultaneously, the deaerator vents (if furnished) should be opened to aid in
cycle deaeration in conjunction with stopping the oxygen feed. At the same time, the heaters (if
furnished) should be carefully vented. The object of the increased ammonia feed rate is to
achieve a pH higher than 9.0. Protection then follows as indicated in Section 3.2 and on the
Figure 3-1 roadmap.
Then, both the oxygen level in the entire cycle and the cycle pH are comparable with those
typical for AVT (feedwater oxygen <10 ppb and pH >9.0). During the longterm shutdown, the
cycle can be regarded and treated as a cycle operated on AVT(2, 4). The only exception is the
already mentioned elimination of the hydrazine or other reducing agent dosing even for a wet
layup. (Use of reducing agents is only permissible in those few combined cycles with copper
alloys in the feedwater systems that need to operate on AVT(R), reducing all volatile treatment.)
4-17
Figure 4-6
Shutdown Chemistry Guidance for Drum Type Evaporator Circuits using OT Chemistry:
Intermediate, Longterm and Extended Shutdowns
4.6.4 Emergency Shutdown
In case of an emergency shutdown for reasons of a technical fault (e.g., defects in the electrical
equipment, an HRSG tube failure), the unit is shut down with the optimum operating chemistry.
If it is foreseeable that the unit will be brought back into service very fast (e.g., overnight or over
a weekend), additional chemical measures are unnecessary. In case the shutdown will continue
for a longer period of time (e.g., several days or longer), the replacement of oxygen containing
water with an oxygen free (<10 ppb oxygen) ammonia treated water (pH >9) makes sense.
Customary layup procedures (Section 3) have to be employed for prolonged shutdowns.
4.6.5 Shutdown as a Result of a Serious Chemistry Excursion
4-18
4.7 Oxygenated Treatment for Once-Through HRSG Circuits
feedwater to this circuit is provided by a low pressure evaporator. The design includes a
condensate polisher or filter in some but not all cases; this equipment, when present, may only be
sized to handle full flow during startup of the unit.
With oxygenated treatment (OT), careful control of the cation conductivity of the feedwater and
evaporator water is required. (5) Increases in the cation conductivity in the presence of oxygen
can result in corrosive conditions, and thus require immediate attention. Thus, consistent with
practice in conventional boilers using OT, it is necessary to stop oxygen feed at least one hour
prior to shutdown. Depending on the expected duration of the shutdown, the pH may also be
adjusted through addition of ammonia. These actions, in combination with any needed changes
in unit operation result in AVT chemistry conditions in the cycle. The only exception is that the
pH need not be increased for short term shutdowns.
Most of the guidance given in Section 4.6 for units with drum type evaporators using oxygenated
treatment (OT) is also applicable to once-through units. As in all once-through evaporators
control of evaporator water purity cannot be achieved by blowdown; any impurities that do not
form deposits in the evaporator circuit will enter the steam path. Thus contamination incidents
normally require immediate shutdown to protect the superheater and reheater circuits and the
steam turbine. Protection of the turbine is vitally important following such events.
4.7.1 Shutdown Procedures
Hydrazine and other reducing agents should never be utilized in units operating on OT. The first
guiding principle (see Section 2.3), clearly indicates that adding such treatments at shutdown or
during layup is inadvisable, as such action would change the potential of the water. The preferred
shutdown practice is to stop the oxygen feed at least one hour before shutdown and, dependent
on anticipated shutdown duration shutdown, to increase the pH in the cycle. Oxygen addition
must be stopped for all types of shutdowns. In order to exclude the possibility of oxygen in-
leakage into the shutdown unit by way of leaking valves, a physical disconnection of the oxygen
supply from the oxygen dosing line is advised.
In many respects, the shutdown considerations are essentially the same as outlined in the road
map for a once-through evaporator circuit operated on AVT Figure 4-5, as discussed in Section
4.4. However, action must first be taken to modify the chemistry (secure oxygen feed and adjust
ammonia feed if needed) and unit operations (system vents) prior to shutdown.
4-19
4.7.2 Short Term Shutdown
Figure 4-7 graphically depicts guidance for chemistry adjustments required for short and
intermediate term shutdowns where the pressure does not decay to atmospheric or oxygen will be
excluded from the water by other means. Guidance(5) consists simply of stopping oxygen feed at
least one hour before shutdown of the unit. Deaerator vents (if furnished) should be opened to
aid in cycle deaeration in conjunction with stopping the oxygen feed. At the same time, any
heaters (if furnished) should be carefully vented. Shutdown of ammonia feed should occur
simultaneously with unit shutdown.
Figure 4-7
Shutdown Chemistry Guidance for Once-Through Evaporator Circuits using OT
Chemistry: Short Term Shutdowns
4.7.3 Intermediate, Longterm and Extended Shutdown
Figure 4-8 graphically depicts guidance for longterm and extended shutdowns. The guidance(5)
consists of stopping oxygen feed at least one hour before shutdown of the unit and of increasing
ammonia feed rates. Simultaneously, the deaerator vents (if provided) should be opened to aid in
4-20
cycle deaeration in conjunction with stopping the oxygen feed. At the same time, any heaters
should be carefully vented. The object of the increased ammonia feed rates is to achieve a pH
higher than 9.0 in agreement with AVT chemistry guidelines(2, 4).
Then, both the oxygen level in the whole cycle and the cycle pH are comparable with those
typical for AVT (feedwater oxygen <10 ppb and pH >9.0). During the shutdown, the cycle can
be regarded and treated as a cycle operated on AVT(2, 4). Protection then follows as indicated in
Section 3.2 and on the Figure 3-1 roadmap.
Figure 4-8
Shutdown Chemistry Guidance for Once-Through Evaporator Circuits using OT
Chemistry: Intermediate, Longterm and Extended Shutdowns
4-21
4.7.4 Emergency Shutdown
In case of an emergency shutdown for reasons of a technical fault (e.g., defects in the electrical
equipment, an HRSG tube failure), the unit is shut down with the optimum operating chemistry.
If it is foreseeable that the unit will be brought back into service very fast (e.g., overnight or over
a weekend), additional chemical measures are unnecessary. In case the shutdown will continue
for a longer period of time (e.g., several days or longer), the replacement of oxygen containing
water with an oxygen free (<10 ppb oxygen) ammonia treated water (pH >9) makes sense.
Customary layup procedures (Section 3) have to be employed for prolonged shutdowns.
4.7.5 Shutdown as a Result of a Serious Chemistry Excursion
4.8 References
1. Delivering High Reliability Heat Recovery Steam Generators. EPRI, Palo Alto, CA: March
2003. 1004240.
2. Cycle Chemistry Guidelines for Combined Cycle/Heat Recovery Steam Generators (HRSGs).
3. Cycle Chemistry Guidelines for Fossil Plants: Phosphate Continuum and Caustic Treatment.
EPRI, Palo Alto, CA: January 2004. 1004188.
4. Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment. EPRI, Palo Alto, CA:
November 2002. 1004187.
March 2003. 1004925.
4-22
5
STARTUP FOR VARIOUS CYCLE CHEMISTRIES
5.1 Startup Requirements for the Various Cycle Chemistries
A recent EPRI publication(1), covering the operational aspects of heat recovery steam generators
necessary to achieve high reliability, notes that for rapid startups, it is essential to have auxiliary
steam to increase condenser vacuum before the unit is fired. This is necessary in order to permit
use of the high pressure (HP) and hot reheat (HRH) steam bypass systems to control the HP and
HRH pressures shortly after HP steam generation commences. It also affords an opportunity to
check steam purity prior to admission of steam to the turbine.
Early use of the bypasses is also essential to establish cooling flows through the HP superheater
and reheater circuits and then regulate the rate of increase in HP pressure to safely limit the rate
of heating of the thick HP steam drum. During this period, and until the transfer of all steam to
the steam turbine is concluded later in the startup, the HRH steam is conditioned and dumped to
the condenser to preserve demineralized water. Auxiliary steam from an auxiliary boiler or from
another operational unit is required to seal the steam turbine glands and raise condenser vacuum.
For satisfactory chemical operation during startup, it is necessary to prevent excessive oxygen
ingress. The use of deaerated makeup will appreciably reduce oxygen levels during startup. Air
in-leakage must be controlled as additional parts of the heat cycle are under vacuum during low
load operation. Information on measurement and detection of air in-leakage is included in
Appendix C. Use of auxiliary steam to peg the deaerator (if part of the design) will enhance
oxygen removal at this point in the cycle.
Detection and repair of condenser leaks during startup is critical to prevent ingress of harmful
contaminants such as chlorides and sulfates. Condensate polishers can help decrease startup
times but are not commonly provided on combined cycle units.
Also, very few combined cycle plant feedwater cycles include feedwater heaters. When present,
it may be desirable to discard heater drains during initial startup operations to reduce the amount
of iron (and copper, if present) entering the HRSG. If the shutdown and layup of the unit are
properly controlled, heater drains should clear more quickly, than with unprotected shutdowns.
As most combined cycles do not include copper in the feedwater system, oxidizing all volatile
treatment, AVT(O), is suitable for the majority of units, while a few may be able to operate
beneficially with oxygenated treatment (OT). Reducing agents should not be added in cycles
employing these feedwater treatments and ensuing discussions of startup reflect this. (Only units
5-1
Startup for Various Cycle Chemistries
with copper in the feedwater system should apply a reducing agent such as hydrazine to establish
reducing AVT conditions.)
If the HRSG has been stored under nitrogen or filled with ammonia solution, it is necessary to
ensure that this is safely vented or disposed.
Initial startup depends on the layup procedure. If the layup was short term, and the unit was filled
with water treated for typical normal operations, startup can proceed without delay. If the
feedwater system was full of water treated for a longer term layup, as shown in the road map,
Figure 3-1 in Section 3.2, some water may have to be dumped to reduce ammonia to more
appropriate values.
If the unit was laid up dry, the feedwater system and HRSG water touched circuits must be filled
with deaerated high purity water and treated with chemicals (ammonia) to correspond to the
normal operating conditions practiced on that unit.
Startup monitoring is largely accomplished by use of the core instrumentation for each chemistry
as outlined in the EPRI Cycle Chemistry Guidelines for Combined Cycle/Heat Recovery Steam
Generators (HRSGs).(2) At startup, the feedwater may include high levels of iron and silica,
particularly following maintenance outages. Most of the iron and silica often will be present in
the condensate as the surface area of the feedwater system is not extensive. Also, feedwater pH
must be controlled by adjustment of ammonia feed rate thus monitoring of parameters such as
pH, specific conductivity and ammonia consistent with plant capabilities and practices is useful.
Evaporator pressure in drum circuits must be carefully controlled to avoid carryover. Silica,
though not a core parameter, can be troublesome as it can transport to steam and foul the low
pressure turbine during and following startup, so this parameter should also be monitored during
startup.
During early startup, the HRSG feedwater should be closely monitored. The following limits for
the HRSG feedwater should be met before startup:
• Oxygen <100 ppb
• Iron <100 ppb (<30 ppb if the HRSG includes a once-through circuit)
• Silica <50 ppb (<30 ppb if the HRSG includes a once-through circuit)
By following the guidelines and procedures outlined in this section, the concentrations can be
reduced to less than those shown above. Further, the initial measured values should fall as the
startup progresses. Good control will require close compliance with the guidance for shutdown
and layup given in Sections 3 and 4.
During startup, monitoring of the condensate and feedwater must be continued, as well as the
chemistry conditions in all drum evaporator water circuits and steam from all evaporators. EPRI
Cycle Chemistry Guidelines for Combined Cycle/Heat Recovery Steam Generators (HRSGs)(2)
set drum evaporator chemistry limits on the basis of pressure and apply to operating pressures of
600 psi (4.1 MPa) and greater; chemistry in drum evaporator circuits with lower design operating
pressures should comply with target values for operation at 600 psi (4.1 MPa).
5-2
It is also necessary to ensure that temperature ramps are maintained according to equipment
manufacturer's specifications. Monitoring of corrosion product transport (essentially iron) can be
used as a benchmark for assessment of the effectiveness of equipment protection measures. As
the purpose of protection is to both minimize startup times and the total transport of iron to the
HRSG, both grab samples (for startup time) and integrated corrosion product samplers (for
cumulative mass transport assessment) may be useful. Such assessments are useful during early
unit operations to establish baseline conditions and may be implemented as needed, to evaluate
changes in iron transport during the life of the unit.
Evaporator drum pressure in each drum type circuit should remain at a reduced level until all
chemistry limits for normal operation have been reached. Maximum use of blowdown (for drum-
type evaporator circuits) and condensate polishing (if available) will minimize startup times. For
drum type evaporator circuits any addition of trisodium phosphate and/or sodium hydroxide has
to be carefully controlled to ensure that excessive carryover into the steam does not occur. This
is important in cycle designs that do not include a steam bypass system. Operation at reduced
pressures is needed until steam purity and chemistry around the cycle is under control.
The various methods of chemical conditioning of evaporator water are considered in the
following sections in the same order as they appear in the recently revised Cycle Chemistry
Guidelines for Combined Cycle/Heat Recovery Steam Generators (HRSGs)(2).
Since, in some cases, the evaporator circuits of multi-pressure HRSGs may operate on different
chemistries and HRSGs also may include both drum-type and once-through circuits, operators
should consider all of the sections which follow that are relevant to the HRSG of interest, to
ensure that customized startup procedures developed comply with the guiding principles of
Section 2.3, as well as the requirements of Sections 5.2 to 5.7 which follow.
5.2 Startup of Units with Phosphate Continuum (PC) Treatment of Drum

HRSG Circuits
The recently revised HRSG Cycle Chemistry Guidelines(2) contain pressure curves and action
levels which relate various chemical parameters to evaporator circuit operating pressure. During
startups, the initial lower drum pressure permits evaporator water chemical concentrations to be
higher than during normal operation. Also, the cumulative operating hours per year for which the
various action levels can be exceeded are twice the values for cycling units as compared to base
loaded units. The values are specific to low and high level phosphate continuum (PC) treatments,
PC(L) and PC(H).
The ramp to full pressure with a cold start is dependent on component design and stress
limitations. Frequent analysis of the feedwater and evaporator water with early emphasis on
suspended solids and silica is recommended. Suspended solids are a measure of the iron oxide
inventory and the source of deposition and possible subsequent underdeposit corrosion. Silica,
which is most likely to be present after maintenance activity, is monitored out of concern for
turbine deposition.
5-3
Units with HRSG evaporator circuits using PC chemistry should be managed as follows.
• Adjust evaporator chemical feed to take advantage of tolerance for higher alkalinity at lower
pressure.
• Adjust trisodium phosphate feed to support anticipated blowdown rate.
• The use of conductivity measurements will provide an indirect assessment of phosphate
concentrations.
• Anticipate HRSG startup and begin dosing chemicals so that target treatment is in place
when HRSG is fired.
• Maximize blowdown and perform bottom blow (if available) during startup when solids are
at their highest concentration.
• With pressure increases above 600 psi (4.1 MPa) when PC is used in a high pressure circuit,
the phosphate residual should be controlled to a concentration consistent with the HRSG
Cycle Chemistry Guideline(2) values for phosphate versus pressure for PC(L) or PC(H) as
apply.
• Operate deaerator vents as needed to prevent air ingress, consistent with plant design and
availability of auxiliary steam during startup.
• Use makeup water that has low dissolved oxygen levels.
Transition to normal operation may proceed as follows.

• Continue blowdown reduction in 50% increments.
• Adjust phosphate chemical feed to support measured or estimated blowdown rate.
• Increase trisodium phosphate to increase alkalinity. (Monosodium phosphate and disodium
phosphate should not be added with PC chemistry.) In the case that the pH is too high, then
the appropriate action is to increase the blowdown rate.
• Be precise in measuring chemical feed dose.
• Monitor chemical feed pump performance.
• Conserve blowdown since excess suspended solids have been removed, chemical feed is
stable and consistent. Evaporator blowdown should be zero during normal operation with
chemistry in limits.
During cold starts, in order to give added protection against contaminant ingress during the
initial operation, the phosphate concentration may be adjusted to the maximum concentration
permitted by the guidelines for PC. The pH should be maintained at the upper pH limit, adjusted
for ammonia. Failure to account for positive bias of the pH due to the presence of ammonia will
lead to inadequate chemistry. This can result in the HRSG actually operating below the PC
control range and increase the risk of evaporator tube corrosion and failures.
5-4
The evaporator circuit may, if intended to normally operate on PC(L), can start up following the
limits for PC(H) to provide additional chemical during early startup. As pressure increases, the
limits of PC(L) should be applied, after the contamination levels are at or below the
corresponding contaminant vs. pressure curves in the HRSG Cycle Chemistry Guidelines(2).
Heavy blowdown can be maintained throughout the startup until contaminant levels are well
within limits, at which time the blowdown should be isolated. Sodium hydroxide dosing at low
levels (1-2 ppm) can be used to ensure that the necessary pH is maintained even in periods with
an increased blowdown. Avoid dryout in the evaporators and excess carryover of evaporator
water into steam. The blowdown remains isolated during normal operation except in periods of
abnormal contamination.
Depending on the plant, and the shutdown and layup conditions adopted, several steps will be
required for startup (in addition to filling the HRSG following a long shutdown and safely
venting the nitrogen, if used). The steps used during startup will be plant specific and, depending
on the practicality, the following stages should be monitored carefully, at least during a trial
period:
• Feedwater to HRSG, with emphasis on purity and ammonia dosing control
• Pressure raising in HRSG, with emphasis on chemistry control in drum evaporator circuits
• Steam from HRSG circuit, with emphasis on carryover, steam purity and feedwater purity
• Steam to turbine, with emphasis on carryover, steam purity and feedwater purity
• Load raising, with emphasis on attaining limits for full load operation
Operating personnel should avoid making changes to evaporator chemistry in reaction to

chemistry changes following a unit trip (such as depressed or elevated pH). This chemistry
change is normal and is usually the result of chemical "hideout” and “return” phenomena.
Careful evaluation of the trip induced chemistry changes is necessary and it is important to avoid
“chasing” or making frequent adjustments in chemistry in response to such changes. Proper
dosing of phosphate as allowed under PC and the exclusive use of trisodium phosphate (plus
sodium hydroxide if required to maintain pH) tends to minimize these changes. As a rule, any
phosphate hideout return causes a pH increase when only trisodium phosphate is added to the
evaporator circuits.
A road map for startup of units with circuits employing PC is given in Figure 5-1.
The road map for startup with phosphate continuum, Figure 5-1, can be divided into five steps:
Step 1 – System Stored Dry (Dehumidified Air or Nitrogen)
If the system has been stored dry (Section 3.2), it should be filled with deaerated water which
meets the HRSG Cycle Chemistry Guidelines for phosphate continuum treated circuits(2).
5-5
Step 2 – System Stored Wet
If the system has been stored wet with a surplus of ammonia and a nitrogen cap as indicated in
Section 3.2, it must be drained under nitrogen and refilled with deaerated water meeting the
HRSG Cycle Chemistry Guidelines for phosphate continuum(2). The startup of the unit can then
proceed.
If the system is returning to service from a short term shutdown without changing the chemistry
and has been protected as indicated in Section 3.2, it is allowable to proceed with startup of the
cycle.
Figure 5-1
Road Map for Startup of Combined Cycle Units with Drum Type Evaporator HRSG Circuits
Treated With Phosphate Continuum (PC) Chemistry
5-6
Step 3 – Feedwater Conditions
The following limits for the feedwater are required prior to raising pressure in the HRSG:
• Oxygen <100 ppb
• Iron <100 ppb
• Silica <50 ppb
During startup following major maintenance, the levels of corrosion products (iron) can be very
high initially, especially if the unit has an air cooled condenser. Silica may also be a problem,
particularly after maintenance activity. It is also useful to monitor these conditions in the
condensate.
Feedwater dosing should be practiced as needed to meet control limits for ammonia.
Feedwater cleanup is possible in units equipped with condensate polishing. When these limits are
attained, raising pressure in the HRSG evaporator circuits can begin consistent with limits for PC
chemistry. Good control of feedwater in the early startup will require close compliance with the
guidelines for unit shutdown and layup.
Step 4 – Chemistry Monitoring
After firing the HRSG, monitoring must be fully implemented, both for chemistry parameters,
and to ensure that temperature ramps are maintained according to the equipment manufacturer's
specifications.
During startup, the concentration vs. pressure curves can be utilized to control sodium, silica,
chloride and sulfate. (Control figures for these constituents in evaporator water are included in
the HRSG Cycle Chemistry Guidelines(2)). Evaporator circuit pressure should remain at reduced
levels such that these limits are maintained before pressure can be increased to the next stage.
Maximum use of blowdown will minimize startup times.
During startup, any chemical excursions must be dealt with quickly and effectively. Increases in
feedwater sodium and cation conductivity may indicate contamination from the makeup system,
contamination from inspection, cleaning and maintenance activities or, most likely, condenser
leakage. The source must be found and the problem corrected at once. Excursions affecting
(lowering) evaporator water pH must be corrected immediately by feeding additional trisodium
phosphate or 1-2 ppm of sodium hydroxide. Avoid dryout conditions in the evaporators and
excessive carryover of evaporator water impurities and conditioning chemicals into the steam.
Effects of cycle contamination are magnified at startup, due to relatively low flow rates for
condensate, feedwater and steam. Cation conductivity may increase as a result of air ingress due
to either aeration of water during the shutdown period or air in-leakage during startup. Shutdown
and layup protection procedures conducted in accordance with the guiding principles of Section
2.3 will minimize these effects during ensuing startups. The change to evaporator water
5-7
chemistry will be minimal compared to contamination involving the makeup system, chemical
cleaning activities or condenser leaks.
Step 5 – Full Load
Full load can be achieved when chemical limits are within the target values for normal operation
given in the HRSG Cycle Chemistry Guidelines for phosphate continuum(2).
5.3 Startup of Units with All-Volatile Treatment (AVT) of Drum HRSG

Circuits
If the evaporator water pH is depressed by contaminants, evaporator circuits can be started on

phosphate continuum chemistry (Section 5.2) using trisodium phosphate additions only or with
caustic treatment (Section 5.5) before gradually converting over to AVT. This period of
adjustment permits the operating staff to ensure, by chemistry monitoring, that conditions are
suitable for the establishment of AVT. The important overriding philosophy here is that
chemicals (trisodium phosphate or sodium hydroxide) should not have to be added to the
evaporator circuits on every startup when operating with AVT; in fact, such requirements are a
possible indication that the chemistry selection is incorrect. Maximum use of blowdown may be
required during startup to minimize contaminant levels in the HRSG. If the carefully controlled
addition of trisodium phosphate or sodium hydroxide extends into the period where the unit is
operating at full (or over) pressure, then special care should be taken that dryout in the
evaporators or excessive carryover into the steam does not occur. Operation at reduced pressures
may be preferable until cycle chemistry is under control.
During off-load conditions, impurities may have been released into the circuit or have entered
from outside, e.g. condenser leaks, CO2 with air ingress. Therefore, during startup, it is important
to consider the effects of these on the feedwater, evaporator water and steam cation conductivity,
silica, sodium, chloride and sulfate concentrations during startup. The oxygen concentration in
the feedwater also requires special consideration. Restrictions will need to be applied to these
parameters, but some relaxation from the normal HRSG Cycle Chemistry Guideline values(2)
may be possible until steady state conditions are achieved.
During startups, the initial lower drum pressure permits evaporator water chemical
concentrations to be higher than those at normal unit operating pressures. Also, the cumulative
operating hours per year for which the various action levels can be exceeded are twice the values
for cycling units, as compared to base loaded units.
It is important to prevent high concentrations of oxygen and chloride in the evaporator water, as
these can act synergistically and may initiate corrosion(3). For this reason, the oxygen
concentration of the evaporator water should not be allowed to exceed 0.2 ppm during operation.
It is also important to ensure that the pH, cation conductivity and chloride concentration are
within the limits given in the HRSG Cycle Chemistry Guidelines(2) for evaporator water.
5-8
period:
At full load, the normal values given in the HRSG Cycle Chemistry Guidelines(2) should be
achieved. There may be room for relaxation, particularly, as regards silica in steam, during
startup and the earlier stages of operation and during low load operation, provided the parameters
are within the HRSG cycle chemistry action levels 1-3. The core parameters, sodium, cation
conductivity and oxygen, given in the HRSG Cycle Chemistry Guidelines(2) should be monitored
in the condensate, feedwater, evaporator water (preferably at downcomer) and steam. The
normal operating levels, as given in the HRSG Cycle Chemistry Guidelines(2), should be
achieved as soon as possible.
A road map for startup of a unit with drum type evaporator circuits operating on AVT is given in
Figure 5-2. The time taken to achieve the required target values will be plant dependent. This
should be determined for each unit, used as guidance for subsequent startups and amended in the
light of operating experience. The procedure can normally be curtailed for warm and hot starts.
5-9
Figure 5-2
Treated All Volatile Treatment (AVT) Chemistry
If the high purity feed and evaporator water conditions can not be maintained during startup, it
may be necessary to resort to another form of chemical conditioning, such as phosphate
continuum or caustic treatment. Operators using AVT should consult the sections of the
guidelines, covering these chemistries if they are used during startup. The selection and
optimization discussion in the HRSG Cycle Chemistry Guidelines(2) provides advice on
determining the optimum evaporator water and feedwater choices for drum HRSG units.
The Figure 5-2 road map can be divided into five steps. The steps are essentially similar to those
described for phosphate continuum treatment in Section 5.2. In drum-type evaporators operating
on AVT, control of evaporator water purity can be achieved by blowdown in drum units.
5-10
meets the HRSG Cycle Chemistry Guidelines for drum type evaporator circuits operating on
AVT(2).
HRSG Cycle Chemistry Guidelines for drum type evaporator circuits operating on AVT(2).
cycle.
• Oxygen <100 ppb
• Iron <100 ppb
• Silica <50 ppb
condensate.
attained, raising pressure in the HRSG evaporator circuits can begin consistent with limits for
AVT chemistry and equipment requirements for temperature ramping. Good control of feedwater
in the early startup will require close compliance with the guidelines for unit shutdown and
layup.
Step 4 – Monitoring
specifications.
During startup, the concentration vs. pressure curves given in the HRSG Cycle Chemistry
Guidelines(2) can be utilized to control conductivity, sodium, silica, chloride and sulfate.
Evaporator pressure should remain at reduced levels such that these limits are maintained before
5-11
pressure can be increased to the next stage. Maximum use of blowdown will minimize startup
times.
contamination from inspection, cleaning and maintenance activities or condenser leakage. The
source must be found and the problem corrected at once. Excursions affecting (lowering)
evaporator circuit water pH may be corrected immediately by feeding trisodium phosphate or 1-2
ppm of sodium hydroxide providing water from this circuit is not used for steam attemperation
or as feedwater to a higher pressure circuit. If such treatment becomes necessary, avoid dryout
conditions in the evaporators and excess carryover of evaporator water impurities into the steam.
Effects of cycle contamination are magnified at startup due to relatively low flow rates for
2.3 will minimize these effects during ensuing startups. The change to evaporator circuit water
cleaning activities, condensate polishers or condenser leaks.
Full load can be achieved when chemical limits are within the HRSG Cycle Chemistry
Guidelines for drum type evaporator circuits operating on AVT(2).
5.4 Startup of Units with All-Volatile Treatment (AVT) of Once-Through

HRSG Circuits
feedwater to this circuit is provided by a low pressure evaporator. The feedwater system
typically does not include provision for circulation and cleanup. The design includes a
condensate polisher or filter in some but not all cases. The once-through evaporator may include
a separator that can be used to remove impurities present in wet steam during the startup period.
Operating startup procedures will reflect the capabilities and requirements of the specific design.
During off-load conditions, deposited impurities may have been released into the circuit or have
entered from outside, e.g. condenser leaks, CO2 with air in-leakage. Therefore, it is important to
consider the effects on the feedwater and steam cation conductivity, silica, sodium, chloride and
sulfate concentrations during startup. Oxygen concentrations in the feedwater also require special
consideration. Restrictions will need to be applied to these parameters, but some relaxation from
the normal HRSG Cycle Chemistry Guideline values(2) should be possible until steady state
operating conditions are achieved.
5-12
period:
• Pressure raising in HRSG, with emphasis on feedwater purity and ammonia dosing control
• Steam from HRSG circuits and feedwater purity
• Steam to turbine and feedwater purity
At full load, the normal HRSG Cycle Chemical Guidelines values(2) should be achieved. There
may be room for relaxation, particularly, as regards silica in steam, during startup, the earlier
stages of operation and during low load operation, provided the parameters are within the HRSG
Cycle Chemistry Action Levels 1-3. (Note that the guidelines are the same for all operating
pressures for once-through evaporators.) The core parameters, sodium, cation conductivity and
oxygen, should be monitored in the condensate, feedwater, and steam, and also pH, silica and
iron, if possible, at least during a trial period. The normal operating levels, as given in the HRSG
Cycle Chemistry Guidelines(2) should be achieved as soon as possible.
A road map showing a scheme for startup of a unit with once-through evaporator circuits
operating with AVT is given in Figure 5-3. The time taken to achieve the required target values
will be plant dependent. This should be determined for each unit, used as guidance for
subsequent startups, and amended in the light of operating experience. The procedure can usually
be curtailed for warm and hot starts.
The road map for startup of once-through HRSG units operating on AVT, Figure 5-3, can be
divided into five steps.
5-13
Figure 5-3
Road Map for Startup of Combined Cycle Units with Once-Through Evaporator HRSG
Circuits Treated All Volatile Treatment (AVT) Chemistry
The steps are essentially similar to those described for HRSGs with AVT drum circuits, except
that for once-through evaporator circuits, control of evaporator water purity can not be achieved
by blowdown, and, the absence of the "reservoir" of the drum and steam separation devices in
once-through designs, means that the acceptable level of impurities is much less than for drum
circuits.
meets the HRSG Cycle Chemistry Guidelines for once-through evaporator circuits operating on
AVT(2).
5-14
HRSG Cycle Chemistry Guidelines for once-through units operating on AVT(2).
cycle.
The following limits for the HRSG feedwater are required prior to raising pressure in the HRSG:
• Oxygen <100 ppb
• Iron <30 ppb
• Silica <30 ppb
condensate.
AVT chemistry and equipment requirements for temperature ramping. Good control of feedwater
in the early startup will require close compliance with the guidelines for unit shutdown and
layup.
specifications.
contamination from inspection, cleaning and maintenance activities, condensate polisher
malfunction or condenser leakage. The source must be found and the problem corrected at once.
5-15
2.3 will minimize these effects during ensuing startups.
Guidelines for once-through circuits operating on AVT(2).
5.5 Caustic Treatment
For cold starts, the ramp to full pressure is dependent on the HRSG/turbine design and stress
limitations. Analysis of the evaporator water suspended solids gives a measure of the magnetite
inventory and the source of evaporator circuit tube deposits. In order to give protection against
contaminant ingress during the initial stages of operation, the concentration of sodium hydroxide
should be maintained within the limits specified in the HRSG Cycle Chemistry Guidelines(2).
Heavy blowdown can be maintained throughout the startup until contamination levels are well
within the specified limits. Care should be taken to avoid excessive sodium hydroxide
concentrations in the evaporator water and carryover of impurities into the steam.
For hot starts, avoid making changes to the HRSG evaporator chemistry and maintain conditions
within the specifications. Avoid dryout in the evaporators and excessive carryover of impurities
into the steam.
Guidance on caustic treatment (CT) for drum type evaporators circuits is given in the HRSG
Cycle Chemistry Guidelines(2).
The basic considerations outlined for startup of units with drum circuits operating on AVT, also
apply to those treated with CT, with the addition that special care has to be taken to prevent any
carryover of sodium hydroxide in the evaporator water, as this could lead to stress corrosion of
austenitic components in the steam circuit. The importance of avoiding the presence of sodium
hydroxide in plants with evaporators that suffer dryout conditions or carryover of evaporator
water into steam can not be stressed too strongly.
As mentioned previously, special care has to be taken to avoid excessively high concentrations
of sodium hydroxide in the evaporator water, and carryover of sodium hydroxide into the steam.
This can be prevented by carefully monitoring sodium in steam. The steps used during startup
will be plant specific and, depending on the practicality, the following stages should be
monitored, at least during a trial period:
5-16
At full load, the normal values given in the HRSG Cycle Chemistry Guidelines(2) should be
achieved. There may be room for relaxation, particularly, as regards silica in steam, during
startup and the earlier stages of operation and during low load operation, provided the parameters
are within the HRSG Cycle Chemistry action levels 1-3. The core parameters, sodium, cation
conductivity and oxygen, should be monitored in condensate, feedwater, evaporator water
(preferably at downcomer), including pH and specific conductivity or sodium hydroxide
concentration, and steam. The normal operating levels, as given in the HRSG Cycle Chemistry
Guidelines(2) should be achieved as soon as possible.
A road map for startup of units with drum type evaporator circuits operating with CT is given in
Figure 5-4. The time taken to achieve the required target values will be plant dependent. This
should be determined for each unit, used as guidance for subsequent startups, and amended in the
light of operating experience. The procedure can normally be curtailed for warm and hot starts.
The road map for startup of drum units operating on CT, Figure 5-4, can be divided into five
steps.
5-17
Figure 5-4
Treated With Caustic Treatment (CT) Chemistry
The steps described in Figure 5-4 are essentially similar to those for drum evaporator circuits on
AVT. Again it should be noted that additional care is required to avoid excessive carryover of
evaporator water impurities and conditioning chemicals (sodium hydroxide) into the steam.
meets the HRSG Cycle Chemistry Guidelines for drum evaporator circuits operating on CT(2).
5-18
HRSG Cycle Chemistry Guidelines for drum evaporator circuits operating on CT(2).
cycle.
• Oxygen <100 ppb
• Iron <100 ppb
• Silica <50 ppb
condensate.
When these limits are attained, raising pressure in the HRSG evaporator circuits can begin
consistent with limits for CT chemistry and equipment requirements for temperature ramping.
Good control of feedwater in the early startup will require close compliance with the guidelines
for unit shutdown and layup.
specifications.
pressure can be increased to the next stage. Maximum use of blowdown and condensate
polishing (if available) will minimize startup times.
contamination from inspection, cleaning and maintenance activities, condensate polisher
malfunction or condenser leakage. The source must be found and the problem corrected at once.
5-19
Excursions affecting (lowering) the evaporator pH must be corrected immediately by feeding 1-2
ppm of sodium hydroxide to the evaporator water. Match the sodium hydroxide to the chloride
concentration. Do not over-feed sodium hydroxide. Avoid dryout in the evaporators and excess
carryover of evaporator water impurities and treatment chemicals into the steam.
cleaning activities, condensate polishers or condenser.
Guidelines for drum units operating on CT(2).
5.6 Startup of Units with Oxygenated Treatment (OT) of Drum HRSG

Circuits
A relatively quick startup after both short term and intermediate term layup is an important
advantage of OT. Usually, due to air ingress during layup, the feedwater and HRSG evaporator
water pH may be reduced. Increased ammonia dosing is required until the feedwater and HRSG
evaporator circuit water pH is stabilized in the normal target value range. Dosing with hydrazine
or other reducing agents is not allowed or required.
Startup is accomplished using essentially the same startup procedure as used for units with drum
circuits on AVT, as discussed in Section 5.3 and summarized in the Figure 5-2 road map. This
road map consists of five steps, resulting in normal operation of the unit on AVT. Because
combined cycle units start up and raise load so quickly, oxygen dosing and other chemistry
changes (reduction of pH in the feedwater and evaporator water) that may be needed to operate
with OT chemistry should not be made until startup under AVT conditions is complete. Effective
venting of external deaerator and heaters (if such devices are part of the design) during the
startup and closure of these vents prior to oxygen dosing is also very important. Oxygen dosing
of the feedwater cannot be resumed until specific chemistry criteria are attained in the feedwater
and the evaporator water of drum evaporator circuits.
For startups following short term layup, there should be no holds or other ramping activities, if
the OT is operated in the optimum fashion according to the HRSG Cycle Chemistry
Guidelines(2). Also, there is normally no need for pH reduction as the pH need not be increased
prior to the shutdown, as discussed in Section 4.6. For startups following longer duration
shutdowns, the feedwater iron levels still should not be a critical parameter. Here the main
monitoring parameters are economizer inlet cation conductivity, oxygen, and pH (by means of
specific conductivity) as well as evaporator water cation conductivity, oxygen, and pH.
5-20
period:
Figure 5-5 shows a road map for startup of drum units operating with OT. The first five steps are
those followed to accomplish startup on AVT. Thesixth step of the road map covers conversion
from AVT to OT, which should only be done after a successful startup has been completed and
all requisite conditions have been met.
meets the HRSG Cycle Chemistry Guidelines for drum type evaporator circuits operating on
AVT(2).
HRSG Cycle Chemistry Guidelines for drum type evaporator circuits operating on AVT(2).
cycle.
5-21
Figure 5-5
Road Map for Startup and OT Conversion of Combined Cycle Units with Drum Type
Evaporator HRSG Circuits Treated With Oxygenated Treatment (OT) Chemistry
5-22
• Oxygen <100 ppb
• Iron <100 ppb
• Silica <50 ppb
condensate.
OT chemistry following short term shutdowns or AVT following longer shutdowns and
equipment requirements for temperature ramping. Good control of feedwater in the early startup
will require close compliance with the guidelines for unit shutdown and layup.
specifications. External deaerators and feedwater heaters, if included in the design should be
vented thoroughly at this time.
pressure can be increased to the next stage. Maximum use of blowdown will minimize startup
times.
source must be found and the problem corrected at once. Excursions affecting (lowering)
evaporator circuit water pH may be corrected immediately by feeding trisodium phosphate or 1-2
ppm of sodium hydroxide providing water from this circuit is not used for steam attemperation
or as feedwater to a higher pressure circuit. If such treatment becomes necessary, avoid dryout
conditions in the evaporators and excess carryover of evaporator water impurities into the steam.
5-23
Step 5 – Operation on AVT
Completion of load raising and normal operation can be achieved when chemical limits are
within the HRSG Cycle Chemistry Guidelines for drum type evaporator circuits operating on
AVT(2). For startup after short term shutdowns, the feedwater and evaporator pH may be at levels
acceptable for OT operation.
Step 6 - Transition to OT
This step, covering conversion of the treatment from AVT to OT should not begin until startup
on AVT has been completed and unit operation is stable. In addition, certain cycle purity
requirements for OT operation must be attained.
A measured feedwater cation conductivity of <0.15 µS/cm is the first precondition for the
transition to OT. Deaerator (if furnished) and heater vents (if furnished) should then be closed for
steady state operation with OT.
A measured evaporator water cation conductivity of <1.5 µS/cm is the second precondition for
the transition to OT. In case of need, the blowdown is used to reduce the evaporator water cation
conductivity.
If the above conditions are not satisfied, the unit has to continue operation with AVT.
Upon initiation of oxygen dosing, dissolved oxygen levels should be monitored at the
economizer inlet and evaporator downcomer sample points. The permissible feedwater oxygen
dose is dependent on the oxygen recirculation ratio (economizer inlet oxygen to downcomer
oxygen); overfeed of oxygen will result in high levels of oxygen in the downcomer. Also, the pH
of the feedwater and evaporator may be reduced if above the levels required for OT operation as
may be needed when returning from long outages. Any external deaerator (if furnished) and
heater vents (if furnished) should then be closed after assuring these vessels have been
effectively vented as required in Step 4.
With oxygen dosing, the chemistry is controlled according to the cycle chemistry guidelines for
OT.(2)
5.7 Startup of Units with Oxygenated Treatment (OT) of Once-Through

HRSG Circuits
feedwater to this circuit is provided by a low pressure evaporator. The feedwater system
typically does not include provision for circulation and cleanup. The design includes a
5-24
condensate polisher or filter in some but not all cases. The once-through evaporator may include
a separator that can be used to remove impurities present in wet steam during the startup period.
Operating startup procedures will reflect the capabilities and requirements of the specific design.
Dosing with hydrazine or other reducing agents is not allowed or required.
Startup is accomplished using essentially the same startup procedure as used for units with once-
through evaporator circuits on AVT, as discussed in Section 5.4 and summarized in the Figure 5-
3 road map. This road map consists of five steps, resulting in normal operation of the unit on
AVT. Conversion to OT chemistry should not be initiated until startup under AVT conditions is
complete and the feedwater confirmed to be of satisfactory purity. Effective venting of external
deaerator and heaters (if such devices are part of the design) during the startup and closure of
these vents prior to oxygen dosing is also very important. Oxygen dosing of the feedwater cannot
be resumed until specific chemistry criteria are attained in the feedwater.
period:
• Pressure raising in HRSG, with emphasis on feedwater purity and ammonia dosing control
• Steam from HRSG circuit and feedwater purity
• Steam to turbine and feedwater purity
For startups following short term layup, there should be no holds or other ramping activities, if
the OT is operated in the optimum fashion according to the HRSG Cycle Chemistry
Guidelines(2). Also, there is normally no need for pH reduction as the pH need not be increased
prior to the shutdown, as discussed in Section 4.7. For startups following longer duration
shutdowns, the feedwater iron levels still should not be a critical parameter. Here the main
monitoring parameters are economizer inlet cation conductivity, oxygen, and pH (by means of
specific conductivity).
Figure 5-6 shows a road map for startup of drum units operating with OT. The first five steps are
those followed to accomplish startup on AVT. The sixth step of the road map covers conversion
from AVT to OT, which should only be done after a successful startup has been completed and
the requisite feedwater purity requirement has been met.
5-25
Figure 5-6
Road Map for Startup of Combined Cycle Units with Once-through Evaporator HRSG
Circuits Treated with Oxygenated Treatment (OT) Chemistry
meets the HRSG Cycle Chemistry Guidelines for once-through evaporator circuits operating on
AVT(2).
5-26
HRSG Cycle Chemistry Guidelines for once-through evaporator circuits operating on AVT(2).
cycle.
• Oxygen <100 ppb
• Iron <30 ppb
• Silica <30 ppb
condensate.
OT following short term shutdowns or AVT following longer shutdowns and the equipment
requirements for temperature ramping. Good control of feedwater in the early startup will require
close compliance with the guidelines for unit shutdown and layup.
specifications. External deaerators and feedwater heaters, if included in the design should be
vented thoroughly at this time.
source must be found and the problem corrected at once.
5-27
Step 5 – Operation on AVT
Completion of load raising and normal operation can be achieved when chemical limits are
within the HRSG Cycle Chemistry Guidelines for once-through evaporator circuits operating on
AVT(2). For startup after short term shutdowns, the feedwater pH may be at levels acceptable for
OT operation.
Step 6 - Transition to OT
This step, covering conversion of the treatment from AVT to OT should not begin until startup
on AVT has been completed and unit operation is stable. In addition, a measured feedwater
cation conductivity of <0.15 µS/cm should be attained before initiating the transition to OT.Until
this requirement is satisfied, the unit has to continue operation with AVT.
Only when the above mentioned precondition is fulfilled (feedwater cation conductivity < 0.15
µS/cm), is oxygenated dosing permitted. Also, the pH of the feedwater and evaporator may be
reduced if above the levels required for OT operation as may exist when returning from long
outages. Any external deaerator (if furnished) and heater vents (if furnished) should then be
closed after assuring these vessels have been effectively vented as required in Step 4.
With oxygen dosing, the chemistry is controlled according to the cycle chemistry guidelines for
OT.(2)
5.8 References
1. Delivering High Reliability Heat Recovery Steam Generators. EPRI, Palo Alto, CA: March
2003.1004240.
3. G. M. W. Mann and R. Garnsey, “Waterside Corrosion Associated with Two-Shift Boiler
Operation on All-Volatile Treatment Chemistry", Corrosion 79 Conference, Materials
Performance, October 1980, pp. 32-38.
5-28
A EQUIPMENT PROTECTION VIA ESTABLISHMENT

OF BARRIER FILMS
As discussed earlier in these guidelines, the most widely used and effective approaches to
equipment protection normally involve wet and dry layup.
Two general types of treatment have been used for equipment protection by establishment of a
barrier between the oxide surface and any water or moisture that may be present. Included here
are the so-called vapor phase inhibitor (VPI) treatments and certain amines, specifically filming
amines; included here are filming amine-neutralizing amine blends, also known as polyamines.
Use of these treatments would appear to meet many of the guiding principles of equipment
protection (Section 2.3) in ways that could be simpler and more cost effective than the traditional
wet and dry layup methods. However, the properties of the chemicals used are not fully
understood and experience with their use for equipment protection in operating plants is limited
or appears impractical. Also, questions exist with respect to possible effects of the chemicals
used to establish barriers on unit operation. Further research would be needed to improve the
understanding of the materials with respect to their suitability for routine use in protection of
steam and water touched surfaces of combined cycle units.
These protection approaches are briefly reviewed in the following subsections but are not
considered further in these guidelines.
A.1 Vapor Phase Inhibitors
VPI treatments encompass a wide range of products for a multitude of equipment and product
protection applications.(1, 2) They have been used for extended storage of HRSGs.(3)
The materials used to protect steam and water touched surfaces of power plant systems are
typically characterized as carboxylic acid salts. The corresponding cations are typically amines,
thus providing a film of material composed of hydrophilic sites adjacent to the surface to be
protected and hydrophobic sites adjacent to the environment.
VPIs used for this application are typically provided in crystalline form and may be added to the
component to be protected manually, though spraying is generally practiced to enhance
distribution of the material. Though typically applied to the surface to be protected while dry
they will also provide protection if dissolved in water. The dry crystals undergo sublimation at
ambient temperatures and may be used to protect wet and dry surfaces as well as the liquid-vapor
interface. Due to their volatile nature, components to be protected must be sealed thoroughly
following addition of the VPI.
A-1
Equipment Protection Via Establishment of Barrier Films
VPIs are available from several manufacturers and suppliers. If the inhibitor is properly applied,
components can reportedly be protected for several months and up to two years, depending on
the local environment and effectiveness of sealing measures. Protection effectiveness can be
assessed by inspection or by use of corrosion coupons of the materials of the component to be
protected.
VPIs used in components such as HRSGs reportedly do not need to be removed from surfaces
before the unit is placed in service. The inhibitors are subject to thermal decomposition at low
temperatures forming volatile compounds which can be removed from the cycle via the vents at
low pressure. Effects of such practice on cycle chemistry during startup are indicated to be
insubstantial though there have been no definitive studies of startup chemistry in high pressure
fossil units.
VPIs are typically and successfully used for other purposes, such as protection of new or
replacement components such as steam generator tubing assemblies, and extended protection
(mothballing) of equipment. Use of VPIs for short term and long term protection of operational
HRSG components would appear to be both time consuming and cost prohibitive. They could be
effectively applied in combined cycle units where extended protection of the HRSG or other
components is required.
A.2 Filming Amines and Polyamines
Filming amines, including the so-called polyamines (high molecular weight filming amines
typically bended with neutralizing amines) have been advocated as a means of equipment
protection under both operational and idle conditions.(4) With respect to equipment protection
during shutdowns, claims have been made that these products can effectively protect surfaces of
equipment that must be drained and opened for inspection. However, the nature of these products
has not been investigated substantially and some concerns exist over their use in high pressure
cycles. These concerns include:
• Possible thermal breakdown in the steam generator
• Effects of treatment overfeed, underfeed or loss of feed on equipment protection, corrosion
product transport, and deposition
• Interactions with other treatment chemicals
• Transient or permanent fouling of condensate polisher or filter media
These concerns are potentially significant, as are their possible benefits, which appear to extend
beyond equipment protection. For instance, use of octadecylamine for the purpose of improving
steam turbine performance was evaluated in a steam turbine at a Russian research facility and
shown to be significant.(5) However, prior attempts to use this treatment in fossil plants caused
operating problems and as a consequence of this negative experience interest in these treatments
was very limited until recent years when the polyamine formulations were introduced.
Polyamine products are now in use in a variety of steam and power generation facilities around
the world; however there are still many questions concerning their use that need to be answered.
Given the fact that a better understanding of these treatments could offer the possibility of an
A-2
Equipment Protection Via Establishment of Barrier Films
easy to implement, effective and inexpensive means of equipment protection during shutdowns,
further investigation to understand the chemistry of filming amines could be a source of
tremendous value to the cogeneration industry.
A.3 References
1. 1. B. A. Miksic, Use of Vapor Phase Corrosion Inhibitors (VCI’s) for the Layup of Power
Plant Equipment”, Proceedings: Fossil Plant Layup and Reactivation Conference. EPRI,
Palo Alto, CA: 1992. TR-101250.
2. 2 B. Miksic, R. Boyle, and B. Wuertz, “Efficacy of Vapor Phase Inhibitor Technology in
Manufacturing”, Corrosion, Vol. 6, No. 60, p. 515-522, NACE International, 2004.
3. 3. W.H. Stroman, S. Maudlin, and D. B. DeWitt-Dick, “HRSG Storage using Vapor Phase
Inhibitor”, presented at the ASME Research Committee on Power Plant and Environmental
Chemistry, 2003 Spring Meeting, West Palm Beach, Florida, April 14-16, 2003.
4. 4. A. Bursik, P. Beezzoli, and A. Graf, “Cycle Chemistry in Cycles with Drum Boilers: Is
there a Niche for the use of Alternative Organic Chemicals in the Continuum of
Treatments?”, Proceedings: Seventh International Conference on Cycle Chemistry in Fossil
5. 5. Turbine Steam Chemistry and Corrosion: Electrochemistry in LP Turbines, EPRI, Palo
Alto, CA: 2001. 1006283.
A-3
B
OXYGEN REMOVAL TECHNIQUES FOR CYCLE
MAKEUP WATER
The Guiding Principles of Section 2.3 clearly indicate the importance of maintaining strict
control to prevent dissolved oxygen and carbon dioxide from entering the heat cycle in order to
minimize corrosion and oxide transport. In contrast with this an EPRI survey conducted in 2000
determined that 44% of the responding organizations put aerated water directly into the cycle,
while 77% put makeup into storage tanks which are vented to atmosphere.(1) A previous survey
on cycle chemistry yielded comparable results.(2) These deficient design and operating
philosophies on makeup water transfer are common in conventional fossil units and are
unfortunately often applied in new combined cycle units. It is obvious that these types of
operating procedures are counterproductive if corrosion is to be fully controlled.
This appendix describes methods by which makeup water can be deoxygenated (and some of
these methods also remove carbon dioxide) and stored in such a way as to prevent further
aeration.
Another important source of ingress of oxygen and carbon dioxide is air in-leakage via
negative pressure in the condenser and low end of the heat cycle. This subject is addressed in
Appendix C.
B.1 Vacuum Deaeration
Vacuum deaeration is a process, which removes both oxygen and carbon dioxide. A typical
vacuum degasifier, which accomplishes this task, is shown in Figure B-1. This equipment
consists of a packed tower with a vacuum pulled from beneath the packing and with water
sprayed over the top of the packing. The water trickles down through the packing, which
provides a large surface area for removal of oxygen and carbon dioxide. The vacuum induces
vaporization of water and produces an upward flow of water vapor together with oxygen and
carbon dioxide. The water is collected in the bottom of the tower and is pumped from there to the
next stage of the system.
B-1
Oxygen Removal Techniques for Cycle Makeup Water
Water inlet
Access and packing
installation opening
Packing
material
Packing removal
connection
Vapor removed
by vacuum pump
Degasified water
storage
Figure B-1
Vacuum Degasifier
The process of vacuum degasification is based on Henry’s Law, which states that the
concentration of a gas in ideal (dilute) liquid solution is proportional to its vapor pressure (or
partial pressure). Therefore, if the pressure over a solution is reduced by a vacuum, dissolved
gases must leave the water and enter the vapor phase to establish a new equilibrium. Increasing
the vacuum increases the degree of gas removal.
The vacuum supply to the degasifier can either be steam jet ejectors or vacuum pumps. The
degasifier is typically located preceding the first anion unit of a demineralizer train in order to
minimize the ionic loading to the anion unit by removing carbon dioxide. Forced draft
decarbonators effectively remove carbon dioxide but saturate the water with oxygen.
Typical removal levels for a vacuum degasifier are: carbon dioxide to 5 ppb and oxygen to 10-20
ppb. Increasing the packing height in the tower and increasing vacuum will result in higher gas
removal.
The vacuum degasifier is quite tall, typically in the range of 25-40 feet (7.6–12.2 m). One reason
for this is to provide room for the packing material and the other is to provide sufficient suction
head for the transfer pump. Because of its height, vacuum degasifiers may be difficult to backfit
into an existing power plant arrangement. This equipment requires considerable maintenance in
order to maintain constant vacuum conditions. In addition, the vacuum equipment is relatively
energy intensive to operate.
B-2
For a typical 300 gpm (1130 L/m) vacuum degasifier unit, the following approximate costs in
year 2005 US dollars, based on an earlier estimate(3), are as follows:
Capital Cost: $142,000.
Installation Cost: $73,500 to $226,000 depending on location and complexity of installation.
Operating and Maintenance (O&M) Cost: 3 to 5% of capital cost per year for normal operations.
B.2 Catalytic Oxygen Removal
The use of hydrazine or other reducing agents to remove oxygen is commonly practiced at many
power plants and is usually fed at the condensate pump discharge or the outlet of the condensate
polisher (if one is installed). The reaction between hydrazine and oxygen can be expressed as
follows:
N2 H4 + O2 → N2 + 2H2O (B-1)
The reaction is stoichiometric, requiring equal amounts of hydrazine and oxygen for the reaction
to proceed to completion. At ambient temperatures this reaction proceeds very slowly. However,
in the presence of a catalyst, such as activated carbon, the reaction proceeds rapidly. Therefore,
this technology can and is being used to remove oxygen from makeup water. The equipment
consists of a vessel containing activated carbon to which hydrazine is fed using a positive
displacement chemical pump. The process was patented (4) by a contract water treatment service
provider and is said to achieve makeup oxygen concentrations less than 10 ppb.
Overall costs in UD dollars for the catalytic process are about $1.30 to $1.85 per 1000 gallons
(approximately $0.34-$0.49/1000 L) depending on system flow rates.
This catalytic process can treat the water either going to storage or coming from storage.
However, when large quantities of water are required, such as during startups, it may be
impractical to provide equipment of sufficient size to meet such demands when processing water
from storage.
One disadvantage of this catalytic process is that carbon dioxide is not removed. Therefore, when
used in demineralizer systems treating waters high in bicarbonate alkalinity, operating costs can
be expected to be substantially higher than when using a vacuum degasifier, for example.
However, when the catalytic systems are used in conjunction with a membrane system, both
carbon dioxide and oxygen can be simultaneously removed (see discussion which follows under
membrane systems).
Another disadvantage associated with the carbon bed system is that an ion exchange bed is
required to remove excess hydrazine and carbon leachables from the effluent stream.(4) Another
possible concern relates to the use of hydrazine, a reducing agent. Extreme overfeed of hydrazine
(or any alternative reducing agent applied for the purpose of catalytic oxygen removal from the
makeup) could result in introduction of water with a negative (reducing) potential to units
B-3
operated under oxidizing conditions. Such action would violate the Guiding Principles of Section
2.3.
B.3 Gas Transfer Membrane Systems
Membrane systems are presently utilized today for many applications, including reverse osmosis,
ultrafiltration, microfiltration, and electrodeionization. Another membrane process, which is
achieving popularity in water treatment applications, is the use of gas transfer membrane (GTM)
technology. Contract water treatment service providers now typically use this technology in
favor of catalytic oxygen removal.
The membranes used for the removal of oxygen and carbon dioxide from makeup water are
constructed of an array or bundle of hollow fiber hydrophobic polypropylene membranes which
are gas permeable and water impermeable. The hollow fiber configuration, with the gas phase
inside the fiber and the liquid phase outside, provides high surface area for maximum efficiency
for gas removal processes. One such design encloses the hollow fiber array within a pressure
vessel, which includes an internal baffle to promote turbulent flow and mass transfer. An
example of this equipment is shown in Figure B-2.
Vacuum and/or Sweep gas

sweep gas
Distribution Baffle Cartridge

tube
Aqueous Aqueous
stream stream
Hollow fiber Collection Housing

membrane tube
Figure B-2
Components of a GTM Unit
B-4
By altering the partial pressure of a gas at the air/water interface, a driving force is created which
results in the mass transfer of a gas into or out of solution. There are three ways to alter the
partial pressure of a gas in a GTM system:
• Apply a vacuum to the inside of the hollow fiber
• Use a “sweep” gas, usually nitrogen, which effectively lowers the partial pressure of other
gases such as oxygen and carbon dioxide
• Use both a vacuum and a “sweep” gas
The effectiveness of this membrane technology is governed by several factors:

• Water flow through the system
• Water temperature
• Amount of vacuum applied
• Volume and purity of the sweep gas
GTM systems can be skid mounted and installed easily in a minimum of space. One such
system(5) consists of two 1x1x1 (3 in series) arrays on two skids which produce a combined
effluent of 200 gpm (760 L/m) at 15 ppb (or less) of dissolved oxygen. The two skids each
occupy less than 370 cubic feet (10.5 m3) of space.
The GTM process is installed on a variety of systems ranging from 0.5 gpm to over 2500
gpm.(6,7)
Overall costs in US dollars for the GTM process are estimated to be about $0.70 to $1.30 per
1000 gallons ($0.18-$0.34 L) depending on the degree of oxygen removal required and the
systems flow rate.
B.3.1 Early GTM Applications Experiences
With a suitably designed system, oxygen levels of less than 1 ppb in the effluent water stream are
said to be achievable. An example of a GTM system used to remove oxygen from boiler feed
water at a petroleum refinery (8) is shown in Figure B-3. In this case, two parallel trains of GTM
units are provided, each having 10 inch (25.4 cm) membrane contactors connected in series. The
nitrogen sweep gas is 99.9% pure, and flows at a rate of 1.5-2.0 scfm. Vacuum requirements are
~ 25 acfm at 28 inches (71 cm) of mercury. The 200 gpm (760 L/min) of product water contains
less than 15 ppb of dissolved oxygen.
An example of a hybrid system employing GTM for carbon dioxide removal followed by
catalytic oxygen removal (9) is shown in Figure B-4. This is an outsourced treatment plant in use
at a nuclear facility.
B-5
99.9% N2
Reverse
osmosis
1 2 3
Municipal water
150 - 390 gpm Product
Concentrate
GTM Skid #1 water
Vacuum 200 gpm
99.9% N2
Ion Activated 5µ
exchange carbon depth
softening filter Reverse
osmosis
1 2 3
Concentrate
GTM Skid #2
Vacuum
Figure B-3
GTM System Process Flow Diagram (Note: 1 gal = 3.785 litres)
Hybrid Deoxygenation System

Anthracite Reverse GTM skid Carbon catalyst
filters osmosis
Sweep
Well Storage air
water tank and
pump
Vacuum
RO reject pump Hydrazine
Mobile Ion Exchange Polisher
Up to 300 gpm
<5 ppb D.O.
Figure B-4
GTM System Process Flow Diagram (Note: 1 gal = 3.785 liters)
B-6
This GTM system consists of three skid-mounted contactors in parallel, a vacuum pump, valving
to allow an air sweep, and instrumentation to monitor vacuum level and air sweep volume. The
membrane system is primarily for carbon dioxide removal, but also removes some oxygen. (The
use of an air sweep rather than nitrogen probably limits the extent to which oxygen can be
removed in this part of the system).
Hydrazine injection occurs at the GTM effluent using a small, diaphragm positive displacement
pump. Any remaining oxygen in the RO permeate water reacts with the hydrazine as it passes
through two activated carbon vessels connected in parallel. The water then enters a three-bed ion
exchange system for further polishing. This system consists of a strong acid cation, strong base
anion and a mixed bed unit.
This hybrid system produces up to 300 gpm (1136 L/m) of purified water at less than 5 ppb of
dissolved oxygen. It is significant to note that the deoxygenated water is stored in a tank with a
nitrogen blanket. The tank effluent is tested daily for dissolved oxygen, which consistently
measures below 5 ppb.
A southwestern electric utility plant chose to utilize gas transfer membrane technology (GTM) to
reduce their dissolved oxygen levels to below 20 ppb prior to their demineralized water storage
tank(10). Their system consists of conventional ion exchange plus GTM to produce 500 gpm
(1894 L/m) of demineralized and deoxygenated water to storage. A unique feature of this system
is that the GTM is located after the strong acid cation and before the strong base anion unit.
Thus, the GTM is acting as a replacement for a forced draft decarbonator to remove the carbon
dioxide generated in the strong acid cation unit. Locating the GTM at this point appreciably
reduces the load on the anion unit while also removing oxygen.
Another innovative use for GTM systems involves minimizing oxygen ingress to an existing
demineralized water storage tank at a nuclear power generating facility(11). In this installation the
inlet water to the tank has been previously deoxygenated to less than 10 ppb. The tank is
equipped with a bladder to minimize oxygen ingress. However, without continuous oxygen
removal, storage tank dissolved levels would gradually reach 1-2 ppm or greater. A GTM system
was installed on a constantly recirculating “kidney loop” in a full-flow 100 gpm (26 L/m) pilot
plant test. Dissolved oxygen levels in the storage tank were then consistently maintained to less
than 10 ppb.
The conclusion reached from the full flow pilot plant test was that a recirculating GTM system is
a viable alternative to installing a nitrogen blanket, floating roof or diaphragm for maintaining
low levels of dissolved oxygen in a storage tank.
B.3.2 Use of GTM Systems in Combined Cycle Units
In general, combined cycle plant designs make no special provision for removal of treated
makeup as part of the treatment process or in storage tanks. However, operating experience and
the requirement that many combined cycle units be operated in cycling/peaking service has
resulted in considerable interest in GTM technology, with some plants now employing it or
considering its installation and use.(12-14)
B-7
Lincoln Electric System (LES) owns and operates three combustion turbine (CT) units which
operate with natural gas or fuel oil at the Salt Valley Generating Station (SVGS). Two of these
units can operate in a combined cycle configuration; each unit has a heat recovery steam
generator (HRSG) that removes heat from the CT exhaust gas and generates steam that is used to
generate power from a steam turbine.
The combined cycle units at SVGS were designed for cycling service operation. During summer
peak demand, it is common for the combined cycle units to operate during the day and shut down
each night. At other times, the units are not normally in service except as needed to meet system
(customer) power demands or to supply power to the grid. Thus these units are subject to both
frequent overnight outages and extensive idle periods. However, it is important that the units be
capable of rapid return to service without impacts on their long term availability.
Makeup water to the combined cycle units is produced on-site and is stored in an outdoor
225,000 gallon (850 m3) stainless steel storage tank that is vented to atmosphere. It is produced
from effluent water discharged from the City of Lincoln’s Northeast Waste Water Treatment
facility. The makeup water treatment system consists of two multi-media filters, two ultra-
filtration skids, two two-pass/two-stage reverse osmosis skids, one electro-deionization skid, and
two mixed bed ion exchangers.
Treated makeup is transferred from the outdoor storage tank to two, 15,000 gallon (56.8 m3)
condensate storage tanks (CSTs). The CSTs are located indoors and are vented to atmosphere.
They supply the makeup water to the combined cycle portion of the plant based on low
condenser hotwell water level. The tanks also periodically receive “dump” water from the
condenser hotwell during plant startups and shutdowns. This water is treated with ammonium
hydroxide. The cycle includes a deaerating condenser with redundant vacuum pumps, which
represents the only means of oxygen removal.
Best operating practices at SVGS require that dissolved oxygen at the condensate pump
discharge from the hotwell to the HRSGs be less than or equal to 7 ppb and the cation
conductivity be less than or equal to 0.3 µS/cm.(12) These requirements become difficult to meet
when the hotwell makeup valve cycles open and closed admitting air saturated water from the
CST’s. As a result, dissolved oxygen (DO) levels have been observed to spike from < 10 ppb to
between 70 and 100 ppb and often do not stabilize before the make-up valve reopens. Feedwater
cation conductivity is rarely less than 0.3 µS/cm due to entrained carbon dioxide (CO2).
When filling empty HRSGs for cold startup or when making up during hot or warm startups, it is
generally necessary to supply the HRSGs with air saturated water, which is recognized to be
undesirable.
In view of these observations and concerns, LES personnel initiated action to identify, evaluate
and compare possible remedial measures that would minimize the effects of air in the makeup
water on cycle chemistry during cycling service and startup operations.(12) Specific needs were to
be able to remove oxygen during transfer from the CSTs to the units during service and to
remove oxygen from water in storage prior to filling empty HRSGs and other combined cycle
system components. Two technologies were evaluated for oxygen removal. The first, nitrogen
B-8
sparging, strips oxygen and other non-condensable gases from water in storage. This system can
also be used to create a nitrogen cap or blanket over the water, thus preventing entry of air
through the vents. The second technology, gas transfer membranes (GTMs), can remove oxygen
from water during transfer or, with suitable piping and pumping, can remove oxygen from water
in storage. Based on considerations of technical performance, operational flexibility and costs,
the GTM system was selected for use at SVGS.
At the time of publication, final system specifications were being developed.(12) LES had
previously investigated prepackaged GTM systems and provision of GTM treatment from a
service organization and ultimately decided to purchase the membrane contactor assemblies and
mounting hardware directly from the manufacturer. The on-site skid, piping, valves,
instrumentation and controls will be engineered, installed and tested by LES personnel. The time
interval from ordering of equipment to initial system operation is estimated to be about 90 days.
The system design will utilize both a vacuum pump and application of nitrogen sweep gas to
remove oxygen from the water. The system will be sized to match the flow rates of the pumps
used to transfer condensate from the CSTs to the hotwells of the units. It will also include a
recycle capability to allow deoxygenation of water to be used to fill equipment for cold startup.
B.4 Makeup Water Storage
The results of oxygen removal by any of the above are completely negated if the makeup water
is stored in tanks, which are vented to atmosphere. There are several ways that tanks can be
equipped to prevent air ingress:
• Plastic or rubber diaphragms
• Floating covers
• Nitrogen positive pressure purging
The use of plastic or rubber diaphragms to protect condensate storage tanks from oxygen ingress
has been very limited in the electrical generating industry. This is the result of relatively high
installed costs, high maintenance costs and the fear (perhaps justly so) that the diaphragm might
fail causing a major disruption in power plant operations. Also, diaphragms would be difficult,
and possibly impossible to install in existing tanks.
Floating covers have been in use, especially in petroleum refinery tanks, for many years. Their
purpose in this case is to prevent undue evaporation of volatile liquids. Here again, installation of
floating covers has not been popular at electrical generating plants for some of the same reasons
as given above for diaphragms. Backfit of floating covers on existing condensate tanks, while
perhaps possible, would certainly require considerable engineering and would undoubtedly be
quite expensive.
B-9
As described earlier, GTM systems have been applied to control dissolved oxygen levels of
water in storage. Another effective means to prevent oxygen ingress to makeup and condensate
storage tanks is to provide a nitrogen blanketing system. Such a system is relatively easy to
install on existing tanks and inexpensive to operate, given the low cost of nitrogen and the
modest amount of nitrogen required.
One such system(15) is shown in Figure B-5. This system has a nitrogen bottom sparger (A), inlet
pipe sparger (B), nitrogen supply and controls (D), oxygen or conductivity analyzer (F), tank
pressure control (C), and an overflow pipe (E). The sparging itself is through sintered stainless
steel sparging elements. Two pressure regulators control the nitrogen pressure to the spargers;
one for the bottom sparger and one for the inlet pipe sparger. This is followed by a passive
critical orifice flow element. This element prevents the nitrogen flow from exceeding the
capacity of the tank pressure control siphon, which vents the excess pressure.
By placing a sparger in the inlet water supply line to the tank, any residual dissolved oxygen in
that water should be effectively removed. Providing a second sparger in the bottom of the tank
will prevent the ingress of air.
The following costs are updated cost estimates(15) for the system shown in Figure B-5 in year
2005 US dollars:
Capital Cost: $23,000 to $33,500.
Installation Cost: $6,000 to $11,500.
Nitrogen Consumption Costs: $120 per month assuming storage tank inflows and outflows are
not excessive.
B-10
C Sparging
element
E
Top View
Pipe
support
Inlet Sparging element
B
Outlet A
Orifice
F
Regulator
D
Option
Figure B-5
A Storage Tank Nitrogen System and Sparging Elements(15)
The system in Figure B-5 would most probably use cylinder nitrogen, because of the relatively
low consumption. The purity of cylinder (or cryogenic) nitrogen is 99.995%.
Other, simpler nitrogen blanketing systems merely provide a slight positive pressure in the
storage tank by using a small continuous flow of nitrogen applied at the top of the tank. This
design, as compared to the above, probably requires a larger consumption of nitrogen and lacks
the obvious advantage of the purge system for incoming water to the tank.
While removal of oxygen from makeup may appear costly at first glance, it is essential to the
proper control of iron and especially copper in the feedwater cycle. In the overall picture, the use
of deaerated makeup water will produce savings, since corrosion and iron oxide transport will be
reduced.
B-11
B.5 References
1. Utility Survey Results. Proceedings: Sixth International Conference on Fossil Plant Cycle
Chemistry, EPRI, Palo Alto, CA: 2001. 1001363.
2. Utility Survey Results. Fifth International Conference on Fossil Plant Cycle Chemistry,
EPRI, Palo Alto, CA: 1997. TR-108459.
3. S. Dominick, U.S. Filter Corporation, Personal Communication to A. Aschoff, August 2000.
4. R. C. Dickerson, W. S. Miller. U. S. Patent 4,556,492, “Deoxygenation Process”. December
3, 1985.
5. Ecolochem, Inc. Application Bulletin, December 5, 1999.
6. D. Schwarz, “TOC Reduction Using Membrane Technology”, Ultrapure Water, October
2000.
7. T. Dang, D. S. Huntsberger and B. A. Kitteringham, “Using Membrane Contactors for CO2
Removal to Extend Resin Bed Life”, Ultra Pure Water, July/August 2003.
8. P. H. Kinghorn and W. E. Haas, “Low Level Deoxygenation of Boiler Makeup Water Using
Gas Transfer Membranes”. Proceedings of the International Water Conference, p. 527,
October 18-20, 1999.
9. S. B. Gorry, W. E. Haas, and J. W. Mahaffee, “Effective Deoxygenation by a Process
Combining Gas Transfer Membranes with Catalytic Oxygen Reduction”. Proceedings of the
International Water Conference, p. 535, October 18-20, 1999.
10. R. M. Mode, W. E. Haas and W. Greene, “Dissolved Oxygen Reduction by Membrane
Technology to Reduce Feed Water Corrosion”. Proceedings of the International Water
Conference, p. 406, October 20-24, 2002.
11. J. Helmrich, W. E. Haas and J. E. Staton, “Maintaining Storage Tank Dissolved Oxygen
Levels Utilizing Gas Transfer Membranes”. Proceedings of the International Water
Conference, p. 207, October 22-26, 2000.
12. Personal communications between D. Dixon, Lincoln Electric System and K. Shields,
December 2005.
13. Personal communications between P. Pye, SCANA and K Shields, January 2006.
14. Personal communications between H. Campbell, Progress Energy and K. Shields, January
2006.
15. O. Jonas, Jonas Inc., Personal communication with A. Aschoff, April, 2000.
B-12
C
AIR IN-LEAKAGE MONITORING AND CONTROL
C.1 Cycle Air In-Leakage
Continual vigilance must be exercised to prevent air in-leakage to the cycle from those
equipment elements under vacuum at any or at all times. Particular problem areas include pump
seals, LP turbine shaft seals, valve bonnets, threaded joints, and especially the expansion joint
between the turbine and condenser. Monitoring the amount of air in-leakage (flow to the vacuum
pumps) is essential for proper control of oxygen and carbon dioxide. Such monitoring will
determine when an exhaustive effort must be made to find and fix the source of air leakage.
The Heat Exchange Institute recommends that air in-leakage be restricted to no more than 1.0
scfm per 100 MW (1.7 sm3/h per 100 MW) of generating capacity. This same value has been
included in many EPRI Cycle Chemistry Guidelines. Current guidelines, including the revised
chemistry guidelines for combined cycles(1) include air in-leakage as a core monitoring
parameter that should be monitored continuously or once per shift. Maintaining a tight system
with low levels of air in-leakage is necessary to meet the EPRI target value for dissolved oxygen
in condensate (10 ppb).
EPRI survey results from 2003(2) clearly indicate that organizations operating fossil plants place
varying levels of importance on cycle air in-leakage. About 60% of the respondents indicated
that air in-leakage is checked continuously or once per day. The remainder indicated it was only
checked weekly or “as needed”.
This appendix reviews available air in-leakage measurement methods and techniques used to
pinpoint locations at which air in-leakage is occurring.
C.2 Rotameters
Excess air in-leakage not only affects corrosion, metal oxide transport and subsequent
deposition, but can also increase turbine backpressure, which directly reduces electrical
generating capacity. A complete analysis of the effects of air in-leakage on condenser efficiency
was made (3,4) using a multisensor probe. This multisensor probe and its use in measuring air in-
leakage are further described later in this Section C.3.
A rotameter located at the exhaust of the steam jet air ejector or mechanical vacuum pump is
often used to quantify condenser air in-leakage. This was the standard approach at the time older
fossil plants were designed and constructed. Manual readings were planned to be taken, normally
once a shift or at least once a day, however, manpower levels often restrict this. Air in-leakage
can increase and remain at potentially damaging levels for hours or possibly days before the
C-1
Air In-leakage Monitoring and Control
increased level of in-leakage is discovered, since turbine backpressure may not have increased
significantly or noticeably.
Under certain conditions, rotameters provide adequate flow rate measurements of air in-leakage.
However, many factors can affect the accuracy of the readings so obtained, such as debris,
exhauster pulsations, water carryover, etc. Rotameters also have limited range, generally 10:1.
Therefore, most problematic air in-leakages cause the rotameter to be pegged against the high
level stop. Rotameters generally receive very little maintenance and are checked very
infrequently at many plants. In these situations, the operator has no idea of the extent of the air
in-leakage, given the fact that the turbine backpressure rise may appear to be rather small and
insignificant.
In an attempt to mitigate these inherent problems with rotameters, a series of instruments were
developed which featured continuous readouts of air in-leakage. These early continuous
measurement devices had some serious drawbacks, such as not being able to distinguish between
water vapor and air; and, operating under the principle that the condenser exhaust gases were
always at saturation, when in fact, they were not.
C.3 Multisensor Probe
Subsequent development efforts have resulted in commercially available instrumentation, which

apparently has overcome the limitations of earlier designs. One such instrument features a
multisensor probe (MSP), which is installed in the exhaust line between the condenser and air
removal equipment. This device is depicted in Figure C-1.
This instrument directly measures mass properties of the mixture of water vapor and non-
condensable gases in the air removal line from which individual gas properties are discerned
using thermodynamic computations. The instrument is essentially a gas analyzer and total mass
flow meter. By measuring velocity, pressure, temperature, and relative saturation, the instrument
can separate the mass flow of non-condensable gas and water vapor from the combined
properties of the mixture. As a result, several important and useful properties of the gas flowing
in the exhauster suction line are determined, as summarized in Table C-1.
Table C-1
Summary of Parameters Determined with the Multisensor Probe System
• Air In-leakage • Water Vapor Density

• Volumetric Flow • Air Density
• Total Mass Flow • Total Pressure
• Water Vapor Mass Flow • Partial Pressure of H2O Vapor
• Water Vapor/Air Mass Ratio • Partial Pressure of Air
• Relative Saturation • Temperature
C-2
Figure C-1
Multisensor Probe (courtesy of Intek, Inc)
Air in-leakage, as measured by the MSP(3), is the sum of all leak sources entering the
subatmospheric pressure system and subsequently flowing through the exhauster line upstream
of the sensor location. The MSP measures the exhauster capacity (ACFM), which is useful to
gauge the effectiveness of the exhausters to remove the gas mixture from the condenser. The
C-3
MSP, however, does not measure air entering the low pressure system near the condensate pump,
such as at suction valves, input connections, and shaft seals.
Evaluation and analysis of condenser performance and measurement of in-leakage is best

accomplished with the use of more than one probe in the MSP system, as shown in Figure C-2.
Each probe is identified by a number that is used to record performance information and to help
pinpoint possible leak locations, since air in-leakage is removed primarily through the condenser
air removal section closest to the leak. As illustrated in Table C-1 and Table C-2, for a single
bundle two-shell condenser, a self validating arrangement can be established that will allow the
accuracy at all probe locations to be verified.
Figure C-2
Validating Arrangement Multisensor Probe Instrument Schematic
The probe marked “Total” measures flow into the vacuum pump (or air ejector) and
distinguishes between air flow and water vapor flow, making it possible to quantify the
performance of the condenser’s exhausting equipment. A measurement at the pump (or air
ejector) discharge cannot provide this information. This probe also measures the sum of flow
from the A and B condenser shell, providing verification of calibration accuracy of the system.
A multi-probe arrangement provides information that narrows the search for leak sources to a
specific region of the condenser(3,4). The following chart illustrates how the three-probe,
validating arrangement of Figure C-2 would react to various leak locations or failed/faulty
exhauster. Use of additional probes, strategically deployed, can improve detection capabilities.
C-4
Table C-2
Examples of a Three-Probe Air In-leakage Measurement System (1 scfm = 1.7sm3/h)
Leak Location Probe Indications and Plant Dissolved Oxygen (DO)
Low, equal leak on both sides and Normal DO.

exhauster in good operating condition For Mass flow, SCFM, ACFM:
Side A = Side B
Side A + Side B = Common
Total Mass Flow 200-600 lb/hr
Mass Ratio >3 at all locations
Side A Possible elevated DO.

For Mass flow, SCFM, ACFM:
Side A > Side B
Side B normal SCFM but very low mass flow
Side B Possible elevated DO.

For Mass flow, SCFM, ACFM:
Side A < Side B
Side A normal SCFM but very low mass flow
Faulty Exhauster Possible elevated DO.

For Mass Flow, SCFM, ACFM:
Side A = Side B, but low mass flow & ACFM
Note: Side A + Side B = Common
Exhauster capacity can be compared Lower than normal Total Mass Flow
by running 1 pump at a time Mass Ratio <3 at all locations
Center joint seal, loss of gland steam, Possible elevated DO.
or other central location high in For Mass Flow, SCFM, ACFM:
condenser hood Side A = Side B with SCFM high
Mass Ratio <3 at all locations
Table C-3
Some Examples of Observed RheoVac Monitor Measured Data and Corresponding
Identification of Leak Presence and Leak Location Determinations (1 scfm = 1.7 sm3/h)
Conditions Probe Indications of Air In-leak (SCFM)
Normal tight system 1 = 2.5 SCFM

2 = 2.5 SCFM
3 = 5 SCFM
Abnormal, need to locate and fix leaks 1 = 15 SCFM

(dogbone joint seal). 2 = 18 SCFM
Condenser pressure elevated. 3 = 33 SCFM
C-5
C.4 Air In-Leakage Source Identification Methods
Rotameters only provide an indication of the magnitude of air passing through the air removal
system piping. The use of the MSP is helpful in determining the extent of air in-leakage and
providing some guidance relative to where, generally, leaks may be occurring. After initial
assessment efforts, it is then necessary to further determine the exact location of the leak(s). The
primary method typically used for this purpose is inert gas leak detection, by use of a
sophisticated analyzer in conjunction with the selected tracer gas. Other techniques, including
ultrasonic detection and infrared detection have also been considered and seen limited use.
C.4.1 Inert Gas Methods
Air in-leakage testing is done by drawing a sample of condenser off-gas from the exhauster
discharge while releasing the tracer gas at those areas within the vacuum boundary where leaks
may be expected to occur. Since the condenser is under vacuum, the tracer gas migrates into the
condenser shell, and from there it is removed by the air-removal system. A leak is identified
when an off-gas sample containing the tracer gas passes through the analyzing equipment and is
detected.
Some early work in this area involved the use of Freon as the tracer gas. However, use of Freon
was subject to environmental concerns and interest subsequently moved to alternative gases.
Helium has been used as a tracer gas successfully in determining air leaks for many years. The
testing is accomplished by injection of helium at various locations (within the vacuum
boundaries) and detection of helium in the condenser off-gases by use of helium mass
spectrometry. This system is still in use today as the most widely used technique for detecting air
in-leakage. There are some limitations to the use of this technique, however, particularly as
regards sensitivity of response, which is particularly important in the detection and evaluation of
very small leaks.
Other tracer gases have been investigated to address the limitations of helium leak detection.
There has been considerable interest in sulfur hexafluoride (SF6) as it offered advantages over
helium. EPRI initiated research activity to investigate and develop the use of SF6 as a tracer gas
in the 1980s. The fundamental advantage of sulfur hexafluoride (SF6) was that it could be
detected in very low concentrations, as low as 0.1 ppb. By contrast, the lowest detectable
concentration of helium is about 1 ppm. SF6 analysis is about 10-100 times more sensitive than
helium detection. Field testing experience showed that each tracer gas had attributes that could
make it the better choice in specific circumstances.(5)
Recognition of SF6 as a greenhouse gas has raised some concerns within some organizations
about regulatory restrictions on its use within some organizations. However, the technique is still
available and in use. Users of these guidelines interested in use of SF6 are advised to determine if
there are any organizational policies which may prohibit or restrict its use.
The determination of air in-leakage using tracer gases requires a great deal of experience and a
considerable outlay of capital if the necessary equipment is to be purchased. Some organizations
have elected to make the necessary investments in equipment and training of personnel. There
C-6
are, however, service and consulting firms specializing in the on-site evaluation of air in-leakage.
These firms have their own equipment and are well versed in this technology. Updated estimates
suggest a typical plant assessment would likely cost between about $3500 and $5000 (US
dollars)(6); in cases where air in-leakage is affecting plant performance, experience has shown
that the associated benefits (above and beyond those related to the chemistry) of prompt
detection and correction of air in-leakage sources can result in very short payback periods.
C.4.2 Ultrasonic and Infrared Techniques for Air In-leakage Detection
These techniques have seen some use in air in-leakage detection.(7) Limitations associated with
the methods have served to constrain their acceptance within industry.
Ultrasonic detection has been successfully used for detecting air leaks. Pressurized leaks are
fairly easily located using ultrasonic listening devices, however, vacuum leaks are reportedly
somewhat harder to find.(8) Shielding or “blocking” suspect areas from background noise will
improve the evaluation.
Air inleakage seen through an infrared camera will appear as a cool area surrounding a void.
However, if the component surface and the ambient temperature are similar, the area will likely
go undetected when using this technology.
C.5 Fossil Plant Air In-Leakage Management Strategies
Typically, air in-leakage in power plants is managed by one of the available tracer gas
techniques.
C.5.1 Leak Detection Using Helium
One large US utility has developed a formal program to control air in-leakage at each of their
power plants (9). The program starts with a comprehensive written procedure which is
continuously updated as new information is forthcoming and new experiences noted. The
program and its revisions are controlled by central staff and implemented at each plant by the
plant’s performance engineering group. Formal training is given to each participant in the
program.
The program is based on a daily monitoring and recording of air in-leakage at the vacuum pump
or steam jet air ejector exhaust. The instrument presently in use for this purpose is a thermal gas
mass flow meter, costing in the range of $2200 to 3200 each. Air in-leakage at the utilities’
various plants is normally in the range of 2–10 scfm/ 100MW (3.4-17 sm3/h/100 MW),
depending upon unit size, configuration, etc. In addition, close attention is paid to unit
backpressure, an increase of which could indicate increased air in-leakage. Continuous readings
of dissolved oxygen at the condensate pump discharge are carefully reviewed as another
indication of increased air in-leakage.
C-7
At the first indication of increased air in-leakage (above the established base, increased
backpressure, higher dissolved oxygen), a leakage test is initiated. An important part of the
program is the establishment of a checklist, which delineates all of the various sampling points
and their location at each plant elevation. For example, the turbine room sample points are
broken down by directions- north, south, east and west relative to the turbine.
The equipment used for air in-leakage detection is a helium mass spectrometer. The detector is
located at the vacuum pump or steam ejector exhaust. A unique feature of the program is the use
of a wireless video camera, which constantly focuses on the readings of the air in-leakage
detection unit. The results (leakage or no leakage) are transmitted to the operator via a remote
wireless receiver. Thus, only one person is required to conduct a test, minimizing manpower.
The detection instrument has an internal vacuum pump and requires a dry sample for proper
operation. The inlet sample tubing is passed through a cooling coil embedded in ice, followed by
two water traps in series prior to entering the instrument.
Tests start at the top of the unit, working down, since helium, being lighter than air, will rise. If
testing started at the bottom of the unit, the rising helium would be sucked into leaks further up,
severely hampering interpretation of results.
Most tests are conducted at medium, or preferably, at full load, to maximize condenser vacuum
and, subsequently, potential air in-leakage. At times, however, it is necessary to test at low loads
to determine leakage at those areas of the low end of the cycle that are under pressure at high
loads but under vacuum at low loads. An example would be the low pressure feedwater heaters.
Some examples of sampling points which are emphasized in the test procedure are condenser and
condensate pump expansion joints, various flanges and pipe fittings, turbine horizontal shell
flanges, turbine rupture diaphragms, turbine shaft seals, various turbine penetrations, pipe plugs,
valve packings, etc.
Helium is sprayed at each test area at low pressure, about 10 psi (70 kPa), for only about 2-3
seconds to prevent too much helium from escaping, which could result in false readings and
misinterpretations. It is necessary to note any extraneous air currents at a particular sampling
location to prevent helium from “spreading out” and causing false leak indications.
Generally, to save time, a group of adjacent test points are sprayed with helium at the same time.
If there are no leaks found, the next group of test points is sprayed. However, if leaks are
recorded, further tests are required to isolate the offending location. A record of leak location is
made together with the relative intensity of the leak.
Another practice, which is followed on a periodic basis, about once per year, is to flood the
condenser with water to above the tube sheet and to look for water leaks from possible cracks in
the condenser shell, attached piping welds or valve packings. Before performing this operation it
will be necessary to determine explicitly whether the structural supports provided are sufficient
to hold the extra weight of water within the condenser.
C-8
Results of all testing are submitted to the maintenance staff at the plant for necessary repairs,
replacements, etc.
This program has been very effective in reducing oxygen and carbon dioxide from entering the
cycle. Corrosion and corrosion transport have been reduced substantially since the program has
been initiated.
C.5.2 Leak Detection Using Sulfur Hexafluoride
A similar approach to that described for helium could be used with SF6, subject to consideration
of organizational policies on use of this material.
The sensor technology for SF6 is based on the principle of electron capture(10). To remove
oxygen from the gas sample, hydrogen gas is introduced. This mixture enters a catalytic reactor
in which the hydrogen and oxygen react to form water. Figure C-3 is a general view of the SF6
analyzer while Figure C-4 is a schematic diagram showing how the off-gas sample passes
through the analyzer.
As indicated earlier, SF6 can generally be used successfully wherever helium can be used,
although the converse may not always be true and there are situations in which use of helium is
preferred(5). The following guidelines may be applied:
• If unit air in-leakage is in excess of 10 CFM, either gas may be used. If less, SF6 is preferred.
• If the unit is running at greater than 20% turbine power, either gas may be used. If the unit
has no turbine power and the leak is so bad that the unit can not be brought up to any turbine
power level, standard procedure would dictate the use of helium.
• The search for the cause of air leakage below the steam space requires the use of SF6 as the
standard procedure.
• Inspections of units of less than 50MW capacity (steam turbine) should always use helium.
C-9
Moisture
outlet Exhaust
Sample Hydrogen Catalyst Exhaust

flowmeter flowmeter assembly flowmeter
Hydrogen
Pump metering
valve Water
trap
Solenoid
Air valve
metering
valve
Electron
Dessicant capture
dryer cell
7mm Pressure
filter regulator
Hydrogen
supply
Sample
inlet
Figure C-3
Flow Schematic for SF6 Analyzer System
C-10
Sample inlet
Dessicant
Copper cooling tower
coil
Water trap
Air mover
To exhaust
system
SF6 analyzer
Water Exhaust Hydrogen

discharge tank
Strip chart
recorder
Figure C-4
Schematic Diagram of SF6 Sampling System
C.5.3 Use of Multisensor Probe System
Another utility experience highlighting the economic value of finding and repairing air leaks was
reported at an EPRI Conference(8).
Other plants manage air in-leakage through use of multisensor probe (MSP) Systems(4,11), which
may incorporate a thermal gas mass flow meter and other sensors as previously described. Its
reported advantages over any exhauster discharge measurements are: freedom from inadvertent
high output spikes or oscillations; measurement of exhauster capacity degradation caused by
shaft seal leaks, wear or regulation; measurement of the water vapor to air mass ratio which
C-11
triggers the onset of increased condenser pressure caused by air in-leakage and by high
resolution measurement of air in-leakage and other non-condensable gases being removed from
the condenser.
Assessment of the understanding of the shell side dynamics of condensers(11,12) has shown that
condenser defects can cause air blanketing or binding, affecting the condenser’s effective heat
transfer coefficient. These regions are subcooled and have a significant concentration of non-
condensable gases with high partial pressure. Therefore, if present they can contribute greatly to
dissolved gases and corrosion even though measured air in-leakage is low.
C.6 References
2. Utility Survey Results. Proceedings: Seventh International Conference on Cycle Chemistry
in Fossil Plants, June 3-5, 2003, Houston, Texas, EPRI, Palo Alto, CA: 2004. 1009194.
3. J. W. Harpster, Intek Inc., “On Understanding Mechanisms that Control Dissolved Oxygen in
Condenser Condensate.” Proceeding of the 21st Annual Electric Utility Workshop, University
of Illinois, Champaign, IL, May 8-10, 2001.
4. W. H. Stroman and J. W. Harpster “Continuous Monitoring for Condenser Air In-Leakage”
Presented at the 2002 Spring Meeting, ASME Research Committee on Power Plant and
Environmental Chemistry, Charleston, SC, March 11-13, 2002
5. Condenser In-Leakage Guideline. Electric Power Research Institute, Palo Alto, CA.:
TR-112819, 2000.
6. La Porte, Conco Services Corp., Personal Communication to A. Aschoff, April 2000.
7. Condenser Tube Failures, Theory and Practice, Volume 1, Fundamentals. EPRI, Palo Alto,
CA: 2006. 1010188.
8. W.A. Kaufman, “Experiences with Steam Cycle Air Ingress at Alliant Energy Fossil Plants:
Case Studies Documenting the Effects of Air In-Leakage on Steam Plant Operations”,
presented at the EPRI Condenser Technology Seminar, EPRI, Palo Alto, CA: September
2002. 1004116.
9. D. W. Reynolds, Dynegy Midwest Generation, Personal Communication to A. Aschoff,
April 2002.
10. La Porte and R. E. Putman, “The Practical Application of SF6 and Helium for Condenser
Tube and Air In-leakage Detection”. Proceedings of the 19th Annual Electric Utility
Chemistry Workshop, University of Illinois, May 11-13, 1999.
11. J. W. Harpster, “An Overview of a Comprehensive Study of Condenser Shell Side
Dynamics”, EPRI Seminar, San Antonio, TX, Sept. 10–12, 2002.
12. J. W. Harpster, “On a Predictive Condenser Performance Model”, Condenser Technology
Conference, EPRI, Palo Alto, CA: 2005. 1010322.
C-12
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Guidelines For Shutdown Layup and Starting For Combined Cycle

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Cycle Chemistry Guidelines for Shutdown,

Layup, and Startup of Combined Cycle

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Agreement on the back cover.

Final Report, March 2006

EPRI Project Manager

(A) MAKES ANY WARRANTY OR REPRESENTATION WHATSOEVER, EXPRESS OR IMPLIED, (I)

(B) ASSUMES RESPONSIBILITY FOR ANY DAMAGES OR OTHER LIABILITY WHATSOEVER

ORGANIZATION(S) THAT PREPARED THIS DOCUMENT

Electric Power Research Institute

NOTICE: THIS REPORT CONTAINS PROPRIETARY INFORMATION THAT IS THE

This report was prepared by

Electric Power Research Institute (EPRI)

This report describes research sponsored by EPRI.

Results & Findings

Challenges & Objective(s)

Applications, Values & Use

The authors of these guidelines

M. Arnold, Deltak Cororation

H. Campbell, Progress Energy

1 INFLUENCE OF SHUTDOWN, LAYUP AND STARTUP PRACTICES ON

2 APPROACH TO GUIDELINES DEVELOPMENT AND CUSTOMIZATION ............. 2-1

2.4.3 Extended Outages................................................................................................2-10

3 SHUTDOWN AND LAYUP TECHNIQUES FOR WATER AND STEAM

4 SHUTDOWN FOR VARIOUS CYCLE CHEMISTRIES............................................. 4-1

5 STARTUP FOR VARIOUS CYCLE CHEMISTRIES ................................................. 5-1

A EQUIPMENT PROTECTION VIA ESTABLISHMENT OF BARRIER FILMS.......... A-1

B OXYGEN REMOVAL TECHNIQUES FOR CYCLE MAKEUP WATER.................. B-1

C AIR IN-LEAKAGE MONITORING AND CONTROL................................................ C-1

1.1 Cycle Chemistry Management Philosophy

1.1.2 Chemistry Selection and Optimization

1.1.3 Peaking and Cycling Duty

1.1.4 Protection of the Steam-Water Cycle during Idle Periods to Prevent

• Iron and Copper (12%)

1.2 Effects of Deficient Shutdown, Layup and Startup Practices

1.2.1 HRSG Tube Damage

1.2.2.1 Protection of Steam Turbines

1.3 Chemistry Guidelines for Shutdown, Layup and Startup

1.3.1 Purpose and Approach

1.3.2 Guidelines Overview

1.3.3 How to Use these Guidelines

Additional information is included in three report appendices. Appendix A discussed some

2.2 Protection of Water and Steam Touched Surfaces

Approach to Guidelines Development and Customization

passage through such transitions should be approached as a seamless, continual process, as

2.2.1 Protection of Steels

Approach to Guidelines Development and Customization

Approach to Guidelines Development and Customization

Approach to Guidelines Development and Customization

Approach to Guidelines Development and Customization

2.2.2 Protection of Copper Alloys

2.3 Guiding Principles Governing Protection of Cycle Components During

Approach to Guidelines Development and Customization

2. Keep Water from Becoming Oxygenated by the Surrounding Environment.

Approach to Guidelines Development and Customization

Approach to Guidelines Development and Customization

2.4 Unit Outages and Shutdowns

2.4.1 Short Term Outage

Approach to Guidelines Development and Customization

2.4.2 Intermediate and Longterm Outages

2.4.3 Extended Outages

2.4.4 Outages Requiring Plant Mothballing Protection

Approach to Guidelines Development and Customization